JPH04504878A - Method for producing heat-resistant transparent acrylic resin - Google Patents
Method for producing heat-resistant transparent acrylic resinInfo
- Publication number
- JPH04504878A JPH04504878A JP3501368A JP50136891A JPH04504878A JP H04504878 A JPH04504878 A JP H04504878A JP 3501368 A JP3501368 A JP 3501368A JP 50136891 A JP50136891 A JP 50136891A JP H04504878 A JPH04504878 A JP H04504878A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- acrylic resin
- heat
- transparent acrylic
- resistant transparent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004925 Acrylic resin Substances 0.000 title claims description 81
- 229920000178 Acrylic resin Polymers 0.000 title claims description 80
- 238000004519 manufacturing process Methods 0.000 title claims description 62
- 229920000642 polymer Polymers 0.000 claims description 114
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 108
- 238000006243 chemical reaction Methods 0.000 claims description 77
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 75
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 54
- 239000002904 solvent Substances 0.000 claims description 53
- 239000000203 mixture Substances 0.000 claims description 43
- 239000000126 substance Substances 0.000 claims description 38
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 36
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 239000001099 ammonium carbonate Substances 0.000 claims description 30
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 29
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 28
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- -1 ammonia compound Chemical class 0.000 claims description 27
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 27
- 125000003118 aryl group Chemical group 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 26
- 229920001577 copolymer Polymers 0.000 claims description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 24
- 229910021529 ammonia Inorganic materials 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 22
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 22
- 235000019441 ethanol Nutrition 0.000 claims description 22
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 20
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000008096 xylene Substances 0.000 claims description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 101100037762 Caenorhabditis elegans rnh-2 gene Proteins 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 229940057054 1,3-dimethylurea Drugs 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 4
- 239000005695 Ammonium acetate Substances 0.000 claims description 4
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 229940043376 ammonium acetate Drugs 0.000 claims description 4
- 235000019257 ammonium acetate Nutrition 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 239000012780 transparent material Substances 0.000 claims description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims 10
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims 5
- 239000006187 pill Substances 0.000 claims 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 4
- 125000004429 atom Chemical group 0.000 claims 3
- 125000004367 cycloalkylaryl group Chemical group 0.000 claims 3
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 claims 2
- ZWAVGZYKJNOTPX-UHFFFAOYSA-N 1,3-diethylurea Chemical compound CCNC(=O)NCC ZWAVGZYKJNOTPX-UHFFFAOYSA-N 0.000 claims 1
- 230000000704 physical effect Effects 0.000 description 40
- 150000003141 primary amines Chemical class 0.000 description 33
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 17
- 239000012046 mixed solvent Substances 0.000 description 15
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 125000000217 alkyl group Chemical group 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 9
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 8
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 150000003949 imides Chemical group 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 6
- 239000007809 chemical reaction catalyst Substances 0.000 description 5
- 238000012937 correction Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- MJEMIOXXNCZZFK-UHFFFAOYSA-N ethylone Chemical compound CCNC(C)C(=O)C1=CC=C2OCOC2=C1 MJEMIOXXNCZZFK-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000113 methacrylic resin Substances 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- BYBVAYUUISIXJJ-UHFFFAOYSA-N azane;hexahydrate Chemical compound N.O.O.O.O.O.O BYBVAYUUISIXJJ-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 2
- 238000013519 translation Methods 0.000 description 2
- YMVFJGSXZNNUDW-UHFFFAOYSA-N (4-chlorophenyl)methanamine Chemical compound NCC1=CC=C(Cl)C=C1 YMVFJGSXZNNUDW-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- GVPODVKBTHCGFU-UHFFFAOYSA-N 2,4,6-tribromoaniline Chemical compound NC1=C(Br)C=C(Br)C=C1Br GVPODVKBTHCGFU-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- ANOUKFYBOAKOIR-UHFFFAOYSA-N 3,4-dimethoxyphenylethylamine Chemical compound COC1=CC=C(CCN)C=C1OC ANOUKFYBOAKOIR-UHFFFAOYSA-N 0.000 description 1
- PQVHMOLNSYFXIJ-UHFFFAOYSA-N 4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]pyrazole-3-carboxylic acid Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(N1CC2=C(CC1)NN=N2)=O)C(=O)O PQVHMOLNSYFXIJ-UHFFFAOYSA-N 0.000 description 1
- 101100496114 Caenorhabditis elegans clc-2 gene Proteins 0.000 description 1
- GXGJIOMUZAGVEH-UHFFFAOYSA-N Chamazulene Chemical group CCC1=CC=C(C)C2=CC=C(C)C2=C1 GXGJIOMUZAGVEH-UHFFFAOYSA-N 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- 241001072332 Monia Species 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- ZBDZQIKIYZOPMA-UHFFFAOYSA-N [P].ClNC1=CC=CC=C1 Chemical compound [P].ClNC1=CC=CC=C1 ZBDZQIKIYZOPMA-UHFFFAOYSA-N 0.000 description 1
- CACDWRVXMWGLKR-UHFFFAOYSA-N ac1l9mop Chemical compound O.O.O.O.O.O CACDWRVXMWGLKR-UHFFFAOYSA-N 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- AVPRDNCYNYWMNB-UHFFFAOYSA-N ethanamine;hydrate Chemical compound [OH-].CC[NH3+] AVPRDNCYNYWMNB-UHFFFAOYSA-N 0.000 description 1
- PKHHQFAULPTXEW-UHFFFAOYSA-N ethane;prop-2-enoic acid Chemical compound CC.OC(=O)C=C PKHHQFAULPTXEW-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KUWAAZMPJBFLEO-UHFFFAOYSA-N n,n,2-trichloroaniline Chemical compound ClN(Cl)C1=CC=CC=C1Cl KUWAAZMPJBFLEO-UHFFFAOYSA-N 0.000 description 1
- ZDHOYZBANMCKGV-UHFFFAOYSA-N n,n-dibromoaniline Chemical compound BrN(Br)C1=CC=CC=C1 ZDHOYZBANMCKGV-UHFFFAOYSA-N 0.000 description 1
- DADSZOFTIIETSV-UHFFFAOYSA-N n,n-dichloroaniline Chemical compound ClN(Cl)C1=CC=CC=C1 DADSZOFTIIETSV-UHFFFAOYSA-N 0.000 description 1
- ILCQYORZHHFLNL-UHFFFAOYSA-N n-bromoaniline Chemical compound BrNC1=CC=CC=C1 ILCQYORZHHFLNL-UHFFFAOYSA-N 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- MYXKPFMQWULLOH-UHFFFAOYSA-M tetramethylazanium;hydroxide;pentahydrate Chemical compound O.O.O.O.O.[OH-].C[N+](C)(C)C MYXKPFMQWULLOH-UHFFFAOYSA-M 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/48—Isomerisation; Cyclisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるため要約のデータは記録されません。 (57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】 耐熱性透明アクリル系樹脂の製造方法 本発明は、耐熱性透明アクリル系樹脂の製造方法に関する。より詳細には、アク リル重合体に触媒の存在または非存在下にイミド構造を導入することにより、耐 熱性が優れたアクリル系樹脂を製造する方法に関する。[Detailed description of the invention] Method for producing heat-resistant transparent acrylic resin The present invention relates to a method for producing a heat-resistant transparent acrylic resin. In more detail, By introducing an imide structure into the polymer in the presence or absence of a catalyst, the resistance to This invention relates to a method for producing an acrylic resin with excellent thermal properties.
従来、メチルメタクリレート樹脂は透明性、耐候性及び機械的性質が優れており 高性能光学素材、装飾素材、自動車及び電気製品等に用いられたが、メチルメタ クリレート樹脂は熱変形温度が１００℃以下と低いので、耐熱性を要する分野に 使用するには、限界があって耐熱性の向上が要求されてきた。Conventionally, methyl methacrylate resin has excellent transparency, weather resistance, and mechanical properties. It was used in high-performance optical materials, decorative materials, automobiles, electrical products, etc., but methylmethane Acrylate resin has a low heat distortion temperature of 100℃ or less, so it is suitable for fields that require heat resistance. There are limits to its use, and improvements in heat resistance have been required.
一般に、アクリル樹脂の耐熱性を向上させる方法としては、次のようなものが挙 げられる。In general, the following methods are available to improve the heat resistance of acrylic resin. can be lost.
１）アクリル酸、メタクリル酸またはこれらのエステル重合体と１級アミンを高 沸点溶媒中で加熱して反応させる方法（米国特許第２，１４６，２０９号）。1) Acrylic acid, methacrylic acid or their ester polymers and primary amines are highly A method of heating and reacting in a boiling point solvent (US Pat. No. 2,146,209).
２）メチルメタクリレート重合体と１級アミンを水存在下に反応させる方法（米 国特許第３，２８４，４２５号）。2) Method of reacting methyl methacrylate polymer and primary amine in the presence of water (U.S. National Patent No. 3,284,425).
３）アクリル系重合体と無水アンモニアまたは無水１級アミンを押出器中で反応 させる方法（米国特許第４．２４６，３７４号）４）メタクリレート樹脂と無水 アンモニアまたは無水１級ア・ミンを溶媒中で反応させる方法（日本特公昭６３ −３６６９６号）しかしながら、前記の方法（１）によれば、溶媒の沸点が高い ので、イミド化重合体から商業的規模で溶媒を完全に分離することが困難である 。従って、この時、得られるイミド化重合体は着色することになるので、最終の 生成物の透明性が低下する。また、前記の方法（２）では、多量の水を分散媒体 として用いて、イミド化反応を進行させるので、水層と重合体層とが分離して均 一なイミド化重合体を得ることが困難であり、反応がアクリル重合体の軟化点以 上で進行するので、反応生成物の塊が撹拌軸に凝り固まって取り扱いにくい。3) React the acrylic polymer and anhydrous ammonia or anhydrous primary amine in an extruder. (U.S. Patent No. 4,246,374) 4) Methacrylate resin and anhydrous A method of reacting ammonia or anhydrous primary amines in a solvent (Japan Special Publication Act 1983 -36696) However, according to the method (1) above, the boiling point of the solvent is high. Therefore, it is difficult to completely separate the solvent from the imidized polymer on a commercial scale. . Therefore, at this time, the imidized polymer obtained will be colored, so the final Product clarity decreases. In addition, in the above method (2), a large amount of water is used as a dispersion medium. As the imidization reaction proceeds, the aqueous layer and polymer layer separate and become uniform. It is difficult to obtain a uniform imidized polymer, and the reaction exceeds the softening point of the acrylic polymer. Since the reaction proceeds at the top, lumps of the reaction product solidify on the stirring shaft and are difficult to handle.
また、前記の方法（３）では、高粘度重合体とガス状の１級アミンを反応させて イミド化反応を実施するので、均一のイミド化重合体を得ることが困難である。In addition, in the above method (3), a high viscosity polymer and a gaseous primary amine are reacted. Since an imidization reaction is carried out, it is difficult to obtain a uniform imidized polymer.
なお、前記の方法（４）によれば、加水分解を防止するためには、アクリル重合 体、溶媒及びアミンから水分の除去が要求される。According to method (4) above, in order to prevent hydrolysis, acrylic polymerization Removal of water from the body, solvent and amine is required.
ここに、本発明者らは前記した欠点を改善するために鋭意研究した結果、次のよ うな方法をによって耐熱性が優れ、かつ透明なアクリル系樹脂を製造できるよう になった。As a result of intensive research to improve the above-mentioned drawbacks, the inventors have discovered the following. It is possible to produce transparent acrylic resin with excellent heat resistance using this method. Became.
即ち、本発明の目的は、イミド化物質としてアンモニウムバイカポネート及びそ の誘導体を使用し、反応物と生成物とをすべて溶解し得る適当な溶媒を選んで使 用することによって、アクリル系樹脂本来のすべての優れた特性を低下させずに 、透明性と耐熱性とが優れたアクリル系樹脂を製造する方法を提供することにあ る。That is, the object of the present invention is to use ammonium bicaponate and its Select and use an appropriate solvent that can dissolve all the reactants and products. By using acrylic resin, all the excellent properties inherent in , to provide a method for producing acrylic resin with excellent transparency and heat resistance. Ru.
また、更に本発明の他の目的は、イミド化反応時、適当な溶媒とともに一定量の 水を添加することによって、耐熱性が優れ、かつ透明なアクリル系樹脂を製造す る方法を提供することにある。Furthermore, another object of the present invention is to use a certain amount of silane along with a suitable solvent during the imidization reaction. By adding water, we can produce transparent acrylic resin with excellent heat resistance. The goal is to provide a way to
また、更に本発明の他の目的は、イミド化物質としてアンモニウムバイカポネー ト及びその誘導体を使用し、適当な溶媒とともに触媒を添加することによって、 耐熱性が優れ、かつ透明なアクリル系樹脂を製造する方法を提供することにある 。Furthermore, another object of the present invention is to use ammonium bicarbonate as an imidization substance. and its derivatives, by adding a catalyst with a suitable solvent, Our objective is to provide a method for producing transparent acrylic resin with excellent heat resistance. .
また、更に本発明の他の目的は、イミド化反応時、適当な溶媒の存在下に触媒を 添加しつつ、一定量の水を投入することによって、耐熱性が優れた透明アクリル 系樹脂を製造する方法を提供することにある。Furthermore, another object of the present invention is to apply a catalyst in the presence of a suitable solvent during the imidization reaction. Transparent acrylic with excellent heat resistance can be created by adding a certain amount of water while adding An object of the present invention is to provide a method for producing a resin based on the resin.
また、更に本発明の他の目的は、メチルメタクリレート重合体とアンモニア化合 物との反応時、無水条件及び適当な溶媒下で触媒を添加することによって、耐熱 性が優れた透明アクリル系樹脂を製造する方法を提供することにある。Furthermore, another object of the present invention is to combine a methyl methacrylate polymer and an ammonia compound. Heat resistance can be improved by adding a catalyst under anhydrous conditions and an appropriate solvent when reacting with An object of the present invention is to provide a method for producing a transparent acrylic resin with excellent properties.
以下、本発明の詳細な説明すれば次の通りである。Hereinafter, the present invention will be described in detail as follows.
本発明は、アクリル樹脂を、イミド化物質であるアンモニア、１級アミンまたは アンモニアや１級アミンを発生するアンモニア化合物と適当な温度条件及び溶媒 中で、触媒の存在または非存在下で加熱することを特徴とする。耐熱性透明アク リル系樹脂の製造方法であり、ポリ（メチルメタクリレートＸＰＭＭＡ）に１級 アミンを発生させるアンモニア化合物、即ち、次式（ｎ）に表示される、アンモ ニウムバイカポネートまたはその誘導体を、溶媒の存在下に１８０℃乃至３５０ ℃温度の範囲で反応させて、イミド構造をＰＭＭＡに導入することによって、次 式（Ｄに表示される、メタクリルイミド基を含有する重合体を製造するもので、 前記の重合体には、イミド化構造単位が１０重量％以上、好ましくは、２０重量 ％以上、含まれることになる。In the present invention, the acrylic resin is imidized with ammonia, a primary amine, or Ammonia compounds that generate ammonia and primary amines and appropriate temperature conditions and solvents It is characterized by heating in the presence or absence of a catalyst. Heat-resistant transparent acrylic This is a method for producing lyle-based resin, in which poly(methyl methacrylate XPMMA) is An ammonia compound that generates an amine, that is, an ammonia compound represented by the following formula (n). Nium bicaponate or a derivative thereof is heated at 180°C to 350°C in the presence of a solvent. By introducing an imide structure into PMMA by reacting in the temperature range of °C, the following can be achieved. For producing a polymer containing a methacrylimide group represented by the formula (D), The above polymer contains 10% by weight or more, preferably 20% by weight of imidized structural units. % or more will be included.
ＲＮＨ３ＨＣＯ８（ｎ） 式中、Ｒ２、Ｒ２及びＲ８は各々水素原子、または１−２０個の炭素原子により 置換、または非置換のアルキル、シクロアルキル、アリール、アラルキル、アル カリールまたはそれらの混合物を表わす。RNH3HCO8(n) where R2, R2 and R8 are each a hydrogen atom or 1-20 carbon atoms Substituted or unsubstituted alkyl, cycloalkyl, aryl, aralkyl, alkyl Represents kaleel or a mixture thereof.
本発明によるメタクリルイミド基含有重合体は、メタクリルイミド（ジメチルグ ルタルイミド）構造が、アクリル樹脂の分岐鎖に導入されたものである。The methacrylimide group-containing polymer according to the present invention comprises methacrylimide (dimethyl group). lutalimide) structure is introduced into the branched chain of acrylic resin.
ここで、イミド単位を導入するメタクリル重合体は、メチルメタクリレート単一 重合体及びエチレン系不飽和単量体との共重合体、例えば、メタクリル酸エステ ル、アクリル酸エステル、スチレンやα−メチルスチレンまたは無水マレイン酸 等とのメタクリル性共重合体等がメタクリルイミド基含有重合体を生成するため のメタクリル性樹脂として使用し得る。このうち特にメチルメタクリレート単一 重合体、メチルメタクリレートとメチルメタクリレート共重合体、メチルメタク リレートとスチレン共重合体及びメチルメタクリレート−スチレン−無水マレイ ン酸共重合体等が好ましい。前記の共重合体で、メチルメタクリレート単位の含 量が、限定されているものではないが、メチルメタクリレート単位の含量が少な くとも５０重量％以上のものが好ましい。Here, the methacrylic polymer into which imide units are introduced is methyl methacrylate single Polymers and copolymers with ethylenically unsaturated monomers, such as methacrylic acid esters acrylic acid ester, styrene or α-methylstyrene or maleic anhydride Because methacrylic copolymers with etc. produce methacrylimide group-containing polymers. It can be used as a methacrylic resin. Of these, methyl methacrylate alone Polymer, methyl methacrylate and methyl methacrylate copolymer, methyl methacrylate Lylate and styrene copolymer and methyl methacrylate-styrene-anhydrous male Acid copolymers and the like are preferred. The above copolymer contains methyl methacrylate units. The amount is, but is not limited to, a low content of methyl methacrylate units. At least 50% by weight or more is preferred.
メタクリル酸エステルとしては、メチルメタクリレート、エチルメタクリレート 、プロピルメタクリレート、ｎ−ブチルメタクリレート、イソブチルメタクリレ ート、ｔ−ブチルメタクリレート、シクロへキシルメタクリレート、ベンジルメ タクリレート及びアリールメタクリレート等があり、アクリル酸エステルとして は、メチルアクリレート、エチルアクリレート、プロピルアクリレート、ｎ−ブ チルアクリレート、イソブチルアクリレート、ｔ−ブチルアクリレート、シクロ へキシルアクリレート、ベンジルアクリレート及びアリールアクリレートなどが ある。透明度及びイミド化反応の観点から見てみる時、前記のエステル中のＰＭ ＭＡが好ましい。Methacrylic acid esters include methyl methacrylate and ethyl methacrylate. , propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate t-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate There are tacrylates, aryl methacrylates, etc., and as acrylic esters are methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, Tyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclo Hexyl acrylate, benzyl acrylate, aryl acrylate, etc. be. When viewed from the viewpoint of transparency and imidization reaction, the PM in the above ester MA is preferred.
本発明に使用する溶媒は、イミド化反応を阻害せず、かつアクリル重合体とイミ ド化生成物をすべて溶解し得る溶媒が必要である。The solvent used in the present invention does not inhibit the imidization reaction and is compatible with the acrylic polymer and imidization reaction. A solvent is required that can dissolve all hydrogenation products.
また、溶媒の沸点が高すぎると、反応後に溶媒を除去することが難しく、低すぎ ると、反応時、圧力が上昇することになるので、５０℃乃至１６０℃程度の沸点 を持っている溶媒が特に好ましい。従って、メチルメタクリレート重合体の溶媒 としてはベンゼン、トルエン、キシレンなどの芳香族炭化水素化合物、メチルエ チルケトン等のケトン、エチレングリコールジメチルエーテル、ダイグライム、 ジオキサン及びテトラヒドロフラン等のエーテル、メチルアルコール、エチルア ルコール、イソプロピルアルコール、ブチルアルコール等のアルコール類及びジ メチルホルムアミド、ジメチルスルホキシド、ジメチルアセトアミド等がある。Also, if the boiling point of the solvent is too high, it will be difficult to remove the solvent after the reaction, and if it is too low, it will be difficult to remove the solvent after the reaction. As a result, the pressure will increase during the reaction, so the boiling point is between 50℃ and 160℃. Particularly preferred are solvents having . Therefore, the solvent for the methyl methacrylate polymer Examples include aromatic hydrocarbon compounds such as benzene, toluene, xylene, and methyl ether. Ketones such as thiruketone, ethylene glycol dimethyl ether, diglyme, Ethers such as dioxane and tetrahydrofuran, methyl alcohol, ethyl alcohol Alcohols such as alcohol, isopropyl alcohol, butyl alcohol Examples include methylformamide, dimethylsulfoxide, and dimethylacetamide.
前記の溶媒は単独または混合溶媒として使用できる。The above-mentioned solvents can be used alone or as a mixed solvent.
一方、メチルメタクリレート重合体をイミド化させるイミド化物質である、次式 （Ｉ［［）に表示される１級アミンとしてはアンモニア、メチルアミン、エチル アミン、ｎ−プロピルアミン、ｎ−ブチルアミン、ヘプチルアミン、ヘキシルア ミン、シクロヘキシルアミン、オクチルアミン、ノニルアミン、デシルアミン、 ドデシルアミン、ヘキサデシルアミン、オクタデシルアミン、イソブチルアミン 、５ｅｃ−ブチルアミン、ｔ−ブチルアミン、イソプロピルアミン、２−エチル ヘキシルアミン、２−フェニルエチルアミン、アリールアミン、アラニン、ベン ジルアミン、パラクロロベンジルアミン、ジメトキシフェニルエチルアミン、ア ニリン、ブロモアニリン、ジブロモアニリン、トリブロモアニリン、クロロアニ リン、ジクロロアニリン、トリクロロアニリン等を使用し得るが、これはガス状 及び液状として、前記の反応時には、工業的に使用が簡単であり、取扱が容易な 、１級アミンを発生させる固体状アンモニウムバイカポネート及びその誘導体が 使用される。On the other hand, the imidization substance that imidizes the methyl methacrylate polymer has the following formula: (Primary amines shown in I[[) include ammonia, methylamine, ethyl Amine, n-propylamine, n-butylamine, heptylamine, hexylamine amine, cyclohexylamine, octylamine, nonylamine, decylamine, Dodecylamine, hexadecylamine, octadecylamine, isobutylamine , 5ec-butylamine, t-butylamine, isopropylamine, 2-ethyl Hexylamine, 2-phenylethylamine, arylamine, alanine, ben Zylamine, parachlorobenzylamine, dimethoxyphenylethylamine, Nilin, bromoaniline, dibromoaniline, tribromoaniline, chloroaniline Phosphorus, dichloroaniline, trichloroaniline, etc. can be used, but this is a gaseous and liquid, which is easy to use industrially and easy to handle during the above reaction. , solid ammonium bicaponate and its derivatives that generate primary amines used.
ＲＮＨ２（ｍ） 式中、Ｒは水素原子や炭素数１乃至２０で置換されるか、あるいは非買換された アルキル、シクロアルキル、アリール、アラルキル、アルカリールまたはそれら の混合物を表わす。RNH2 (m) In the formula, R is substituted with a hydrogen atom or a carbon number of 1 to 20, or is non-replaced. Alkyl, cycloalkyl, aryl, aralkyl, alkaryl or the like represents a mixture of
反応器内で、メチルメタクリレート樹脂とイミド化物質との反応温度条件は、１ ８０乃至３５０℃、好ましくは２００℃乃至３００℃である。反応温度が３５０ ℃より高いと、メチルメタクリレート重合体の分解反応が起きる。１８０℃より 低いとイミド化反応の速度が顕著に低下して、イミド化工程に長時間が必要であ る。In the reactor, the reaction temperature conditions between the methyl methacrylate resin and the imidized substance are 1. The temperature is 80 to 350°C, preferably 200 to 300°C. Reaction temperature is 350 When the temperature is higher than 0.degree. C., a decomposition reaction of the methyl methacrylate polymer occurs. From 180℃ If it is too low, the rate of imidization reaction will drop significantly and the imidization process will require a long time. Ru.
また、本発明は、メタクリル樹脂を前記の式（ｍ）に表示される、１級アミンま たは１級アミンを発生させるアンモニア化合物と溶媒の存在下に、１８０℃乃至 ３５０℃の温度範囲で反応させるが、イミド化反応の促進剤として水５乃至２０ 重量％を添加して均一に反応させることによって、メタクリルイミド基含有重合 体を製造する。The present invention also provides a method for converting methacrylic resin into a primary amine or a primary amine represented by the above formula (m). or 180°C in the presence of an ammonia compound and a solvent that generate primary amines. The reaction is carried out at a temperature range of 350°C, but water is used as an accelerator for the imidization reaction. methacrylimide group-containing polymerization by adding % by weight and reacting uniformly. Manufacture the body.
前記の重合体中、イミド化構造単位が１０重量％以上、好ましくは２０重量％以 上含まれる。In the above polymer, the imidized structural unit is 10% by weight or more, preferably 20% by weight or more. Included above.
前記の反応に用いられている、反応促進剤中の一つが水であるが、イミド化反応 時、適当量の水を添加すると、これが触媒の役割をして反応が有利に行われる。One of the reaction accelerators used in the above reaction is water, but the imidization reaction When an appropriate amount of water is added, this acts as a catalyst and the reaction is carried out advantageously.
本発明では、適当量の水の存在下に、イミド化率を増加させて、耐熱性が向上し た透明アクリル系樹脂を製造できる。尚かつ、加熱により１級アミンを発生させ るアンモニア化合物を使・用する場合には、水が反応系内で、溶解度を増加させ る作用をして、イミド化反応時、反応性（反応速度）を増加させ役割も行ってい る。従って、メチルメタクリルイミド重合体製造時、水５乃至２０重量％、好ま しくは７乃至１５重量％を添加し、使用するのが好ましい。In the present invention, heat resistance is improved by increasing the imidization rate in the presence of an appropriate amount of water. It is possible to produce transparent acrylic resin. Furthermore, primary amines are generated by heating. When using ammonia compounds, water may be present in the reaction system to increase solubility. It also plays a role in increasing the reactivity (reaction rate) during the imidization reaction. Ru. Therefore, when producing methyl methacrylimide polymer, 5 to 20% by weight of water is preferably used. It is preferable to add and use 7 to 15% by weight.
万一、水を５重量％未滴の量に使用すれば、反応性が低下して耐熱性が減少し、 かつ２０重量％の超過使用時には、水層と重合体層との分離により不均一なイミ ド化重合体が得られ、生成物が反応器軸に凝り固まるようになる。If water is used in an amount less than 5% by weight, the reactivity will decrease and the heat resistance will decrease. And when used in excess of 20% by weight, uneven imprinting may occur due to separation of the water layer and polymer layer. A hydrogenated polymer is obtained and the product becomes agglomerated on the reactor shaft.
また、本発明は、アクリル樹脂に炭酸水素アンモニウム及びその誘導体を溶媒存 在下に１００℃乃至３５０℃の温度範囲で反応させるが、イミド化反応の促進剤 として、次式（ｒＶ）に表示される、テトラアルキルアンモニウムヒドロキシド を０．０１乃至１５重量％を添加して、均一に反応させることにより、メタクリ ルイミド基含有重合体中に、メタクリルイミド基が５重量％以上含有した重合体 を製造するものである。In addition, the present invention provides ammonium hydrogen carbonate and its derivatives in an acrylic resin in the presence of a solvent. The reaction is carried out at a temperature range of 100°C to 350°C in the presence of an accelerator for the imidization reaction. , a tetraalkylammonium hydroxide represented by the following formula (rV) By adding 0.01 to 15% by weight of methacrylate and reacting uniformly, A polymer containing 5% by weight or more of methacrylimide groups in the limide group-containing polymer It manufactures.
Ｒ４ＮＯＨ（ＩＶ） 式中、Ｒは水素原子または炭素数１乃至２０で置換されるか、あるいは非置換の アルキル、シクロアルキル、アリール、アラルキル、アルカリールまたはそれら の混合物を表わす。R4NOH(IV) In the formula, R is a hydrogen atom, substituted with 1 to 20 carbon atoms, or unsubstituted Alkyl, cycloalkyl, aryl, aralkyl, alkaryl or the like represents a mixture of
反応物質及び反応温度は、前記と同一であり、前記の反応に用いられた反応触媒 としては、テトラアルキルアンモニウムヒドロキシドが適当である所、好ましく はテトラメチルアンモニウムヒドロキシドペンタヒドレート、テトラエチルアン モニウムヒドロキシドが良い。テトラアルキルアンモニウムヒドロキシドは反応 系で、塩基性触媒として作用して反応重合体の反応性を向上させるので、イミド 化率を増加させ、反応条件（反応温度及び反応圧力）を緩和させるので、耐熱性 が向上した透明アクリル系樹脂を製造できる。また、テトラアルキルアンモニウ ムヒドロキシドは、加熱によりトリアルキルアミンとアルコールに分解されるの で、重合体生成物からの分離も容易である。The reactants and reaction temperature are the same as above, and the reaction catalyst used in the above reaction Tetraalkylammonium hydroxide is suitable, preferably is tetramethylammonium hydroxide pentahydrate, tetraethylammonium Monium hydroxide is good. Tetraalkylammonium hydroxide reacts In the system, imide acts as a basic catalyst and improves the reactivity of the reacting polymer. It increases the conversion rate and relaxes the reaction conditions (reaction temperature and reaction pressure), which improves heat resistance. A transparent acrylic resin with improved properties can be produced. Also, tetraalkyl ammonium Hydroxide is decomposed into trialkylamine and alcohol by heating. Therefore, it can be easily separated from the polymer product.
従って、メチルメタクリレート重合体の製造時、テトラアルキルアンモニウムヒ ドロキシドの使用量は０．０１乃至１５重量％、好ましくは０．１乃至７重量％ のものが良いが、万一、テトラアルキルアンモニウムヒドロキシドの使用量が０ ．０１重量％未満の場合には、触媒の添加効果が十分に得られないため好ましく ない。一方１５重量％を超すと物性の低下を招くようになる。Therefore, when producing methyl methacrylate polymer, tetraalkylammonium The amount of droxide used is 0.01 to 15% by weight, preferably 0.1 to 7% by weight. However, in case the amount of tetraalkylammonium hydroxide used is 0. ．． If it is less than 0.01% by weight, the effect of adding the catalyst will not be sufficiently obtained, so it is preferable. do not have. On the other hand, if it exceeds 15% by weight, physical properties will deteriorate.
また、本発明は、アクリル樹脂を前記式（ｍ）に表示される、１級アミンまたは １級アミンを発生させるアンモニア化合物と溶媒の存在下で１００℃乃至３５０ ℃の温度範囲で反応させるが、触媒として前記式（ｒＶ）に表示される、テトラ アルキルアンモニウムヒドロキシド０．０１乃至１５重量％と水５乃至２０重量 ％を添加して、均一に反応させることによって、メタクリルイミド基含有重合体 を製造するもので、前記の重合体中にメタクリルイミド基が、好ましくは５重量 ％以上含まれる。Further, the present invention provides an acrylic resin with a primary amine or a primary amine represented by the above formula (m). 100°C to 350°C in the presence of an ammonia compound and a solvent that generate a primary amine. The reaction is carried out in the temperature range of Alkylammonium hydroxide 0.01 to 15% by weight and water 5 to 20% by weight % and reacted uniformly to form a methacrylimide group-containing polymer. The methacrylimide group is preferably 5% by weight in the polymer. Contains more than %.
本発明は、アクリル樹脂にアンモニア、１級アミンまたはアンモニアや１級アミ ンを発生させるアンモニア化合物を適当の溶媒中で、１００°Ｃ乃至３５０℃の 温度及び無水条件下で反応させるが、反応促進剤として前記式（ＴＶ）に表示さ れる、テトラアルキルアンモニウムヒドロキシドを添加して、均一に反応させる ことにょフて、メタクリルイミド基を含有する重合体を製造するものとして、前 記の重「・ 合体中に、メタクリルイミド基を５重量％以上含有する重合体を製 造するものである。この時、触媒を無水条件下で用いた以外は前記； と同一の 条件で実施した。The present invention uses ammonia, a primary amine, or ammonia and a primary amine in an acrylic resin. An ammonia compound that generates carbon is heated at 100°C to 350°C in a suitable solvent. The reaction is carried out under temperature and anhydrous conditions, and the reaction promoter shown in the above formula (TV) is Add tetraalkylammonium hydroxide and react uniformly. In particular, for producing polymers containing methacrylimide groups, Producing a polymer containing 5% by weight or more of methacrylimide groups during coalescence. It is something that is created. At this time, the same procedure as above was used except that the catalyst was used under anhydrous conditions. It was carried out under the following conditions.
前記のように、本発明の製造方法により、得られたアクリル系樹脂は、本来の優 れた光学的性質、機械的性質、外気の影響を受けない性質、成型加工及び生産性 等を、そのまま維持しつつ従来に比べて耐熱性が数隻向上され、かつ透明性が改 善されるようになる。As mentioned above, the acrylic resin obtained by the production method of the present invention has its original properties. Optical properties, mechanical properties, properties unaffected by outside air, molding processing and productivity While maintaining the same characteristics as before, the heat resistance has been improved several times compared to the conventional model, and the transparency has been improved. Become good.
本発明に従う重合体の物性測定は、次に基づき実施した。Physical properties of the polymer according to the present invention were measured based on the following.
１）重合体のイミド化決定 赤外線スペクトル（Ｂ ｌ０ＲＡＤ製、ＦＴＩＲ）を用いたブロム化カリウム（ ＫＢｒ）ペレット状で測定した。1) Determination of imidization of polymer Potassium bromide ( KBr) Measured in pellet form.
２）重合体のイミド化度（％） この測定は原素分析価（ＰＥＲＫｒＮ ＥＬＭＥＲＭＯＤＥＩ、： ２４ＯＢ） の窒素含有量により計算した。2) Degree of imidization of polymer (%) This measurement is based on the elemental analysis value (PERKrN ELMERMODEI: 24OB) Calculated based on the nitrogen content of
３）耐熱性 これはガラス転移温度（Ｄｕｐｏｎｔ Ｍｏｄｅｌ： １０９０ ）を測定して 検討した。3) Heat resistance This is determined by measuring the glass transition temperature (Dupont Model: 1090). investigated.
以下、本発明を実施例、比較例によって、より具体的に説明するが、本発明がこ れらに限定されないことはもとよりである。Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Of course, it is not limited to these.
実施例Ｉ ＰＭＭＡ ［（株）５ ツキ−１ＩＨ−８３０コ１００重量部、イミド化物質と して炭酸水素アンモニウム７９重量部及び混合溶媒としてテトラヒドロフラン（ ＴＨＦ）２６８重量部とメチルアルコール２６８重量部を３００ｃｃオートクレ ーブに投入した後、この反応の混合物を撹拌しながら、酸化防止のために窒素を 十分に還流させた。次いで、前記の反応の混合物を２５ Ｏｒｐｍで撹拌して溶 解した後、２３０℃で３時間（内圧・ １４７０ｐｓｉ）反応させてがら、反応 の完結後、メタクリルイミド基含有重合体が含まれた溶液をｎ−ヘキサンに沈澱 させ、濾過して真空状態及び１００℃の温度で十分に乾燥して白い粉末状態の重 合体を得た。この時、得られた重合体を赤外線スペクトルで測定した結果、１６ ８０ｃｍ”、１７００ｃｍ−’及び１７２゜ｃｌ’でメタクリルイミド構造の特 性帯が現れてメタクリルイミド重合体を確認した。この重合体の物性測定の結果 は次の表１に示す。Example I PMMA [5 Tsuki-1IH-830 Co., Ltd. 100 parts by weight, imidized substance and 79 parts by weight of ammonium hydrogen carbonate and tetrahydrofuran (as a mixed solvent) 268 parts by weight of THF) and 268 parts by weight of methyl alcohol were added in a 300cc autoclave. After stirring the reaction mixture, nitrogen was added to prevent oxidation. Thoroughly refluxed. The mixture of the above reaction was then stirred at 25 Orpm to dissolve the After dissolving, the reaction was continued at 230°C for 3 hours (internal pressure: 1470psi). After completion of the process, the solution containing the methacrylimide group-containing polymer was precipitated in n-hexane. filtered and thoroughly dried in vacuum and at a temperature of 100°C to form a white powder. Obtained union. At this time, as a result of measuring the obtained polymer by infrared spectrum, it was found that 16 80cm”, 1700cm-’ and 172°cl’. A sex zone appeared and methacrylimide polymer was confirmed. Results of physical property measurements of this polymer are shown in Table 1 below.
実施例２ イミド化物質として炭酸水素アンモニウム（ＮＨ４ＨＣＯ３）６３重量部、混合 溶媒としてテトラヒドロフラン３４０重量部とメチルアルコール１４４重量部、 内圧が８１０ｐｓｉであること以外は前記の実施例１と同様に実施して重合体を 製造し、これらの物性を次の表イミド化物質として炭酸水素アンモニウム４７重 量部、混合溶媒としてテトラヒドロフラン３４０重量部とメチルアルコール１４ ４重量部、内圧が７８０ｐｓｉであること以外は前記の実施例１と同様に実施し て重合体を製造し、これらの物性を次の表１に示す。Example 2 63 parts by weight of ammonium hydrogen carbonate (NH4HCO3) as an imidization substance, mixed 340 parts by weight of tetrahydrofuran and 144 parts by weight of methyl alcohol as a solvent, The polymer was prepared in the same manner as in Example 1 above, except that the internal pressure was 810 psi. The following table shows the properties of ammonium hydrogen carbonate 47% as an imidized substance. 340 parts by weight of tetrahydrofuran and 14 parts by weight of methyl alcohol as a mixed solvent 4 parts by weight, and the internal pressure was 780 psi. Polymers were produced and their physical properties are shown in Table 1 below.
実施例４ メチルメタクリレート（ＭＭＡ）５７重量％、無水マレイン酸（ＭＡＲ）２７重 量％及びスチレン（ＳＴ）１６重量％及び連鎖移動剤としてｔ−ドデシルメルカ プタンオル０．２重量％を添加して１４５℃で２時間溶液重合（溶媒としてはエ チルベンゼン）させて共重合体を得た。Example 4 Methyl methacrylate (MMA) 57% by weight, maleic anhydride (MAR) 27% by weight % and 16% by weight of styrene (ST) and t-dodecylmerca as chain transfer agent. Solution polymerization was carried out at 145°C for 2 hours with the addition of 0.2% by weight of putanol (as the solvent, tilbenzene) to obtain a copolymer.
この時、得られたＭＭＡ−ＭＡＲ−８Ｔ共重合体１００重量部、イミド化物質と して炭酸水素アンモニウム３１重量部、混合溶媒としてテトラヒドロフラン３７ ２重量部とメチルアルコール３６重量部使用し、内圧が７００ｐｓｉであること 以外は前記の実施例１と同様に実施して重合体を製造し、これらの物性を次の表 １に示す。At this time, 100 parts by weight of the obtained MMA-MAR-8T copolymer, an imidized substance and and 31 parts by weight of ammonium hydrogen carbonate, and 37 parts by weight of tetrahydrofuran as a mixed solvent. 2 parts by weight and 36 parts by weight of methyl alcohol are used, and the internal pressure is 700 psi. Except for this, a polymer was produced in the same manner as in Example 1 above, and its physical properties are shown in the table below. Shown in 1.
実施例５ ＭＭＡ重合体１００重量部に、イミド化物質として炭酸水素アンモニウム７９重 量部、テトラヒドロフラン５３６Ｍ量部を使用したこと以外は前記の実施例１と 同様に実施して重合体を製造し、これらの物性を次の表１に示す。Example 5 To 100 parts by weight of MMA polymer, 79 parts by weight of ammonium hydrogen carbonate was added as an imidization substance. Example 1 except that 536 M parts of tetrahydrofuran was used. Polymers were produced in the same manner and their physical properties are shown in Table 1 below.
比較例Ｉ ＰＭＭＡ１００重量部に、単一溶媒としてテトラヒドロフラン３４０重量部をオ ートクレーブ反応器に投入した後、２３０℃で内圧が７０Ｑｐｓｉになるように ガス状アンモニアを添加して反応させて重合体を製造し、これら物性を次の表１ に示す。Comparative example I Add 340 parts by weight of tetrahydrofuran as a single solvent to 100 parts by weight of PMMA. After charging into the autoclave reactor, keep the internal pressure at 230℃ and 70Qpsi. A polymer was produced by adding gaseous ammonia and reacting, and its physical properties are shown in Table 1 below. Shown below.
ＭＭＡ：メチルメタクリレート単量体 ＭＨＡ・無水マレイン酸単量体 ＳＴ ：スチレン単量体 実施例６ ＰＭＭＡ［（株）ラッキー、ＩＨ−８３０コ１００重量部、イミド化物質として シクロアルキルアミン５８重量部、イミド化反応促進剤として蒸留水１００重量 部、混合溶媒としてテトラヒドロフラン４５６重量部とメチルアルコール５８重 量部をオートクレーブに投入した後、反応混合物を撹拌しながら酸化防止のため に窒素を十分に還流させた。次いで、２５ Ｏｒｐｍで撹拌してから溶解して２ ００℃で３時間反応させて、反応が完結した後、メタクリルイミド基含有重合体 を含む溶液をｎ−へキサンに沈澱させ、濾過して真空状態及び１００℃の温度で 十分に乾燥して、白い粉末状態の重合体を得た。MMA: Methyl methacrylate monomer MHA/maleic anhydride monomer ST: Styrene monomer Example 6 PMMA [Lucky Co., Ltd., IH-830 100 parts by weight, as an imidization substance 58 parts by weight of cycloalkylamine, 100 parts by weight of distilled water as imidization reaction accelerator parts, 456 parts by weight of tetrahydrofuran and 58 parts by weight of methyl alcohol as a mixed solvent. After adding aliquots to the autoclave, the reaction mixture was stirred to prevent oxidation. The mixture was thoroughly refluxed with nitrogen. Next, stir at 25 Orpm and dissolve. After the reaction was completed at 00°C for 3 hours, the methacrylimide group-containing polymer The solution containing is precipitated in n-hexane, filtered and treated under vacuum and at a temperature of 100°C. After thorough drying, a white powdery polymer was obtained.
この時、得られた重合体を赤外線スペクトルで測定した結果、１６８０ｃｍ−１ ，１７００ｃｍ−’及び１７２０ｃｍ−’でメタクリルイミド構造の特性帯が現 れてメタクリルイミド重合体を確認した。この重合体の物性測定の結果は次の表 ２に示す。At this time, the obtained polymer was measured by infrared spectrum, and the result was 1680 cm-1 , 1700 cm-' and 1720 cm-', characteristic bands of methacrylimide structure appear. The methacrylimide polymer was confirmed. The results of measuring the physical properties of this polymer are shown in the table below. Shown in 2.
実施例フ イミド化物質として炭酸水素アンモニウム６３重量部、イミド化反応促進剤とし て蒸留水６０重量部、溶媒としてテトラヒドロフラン３４０重量部とメチルアル コール１４６重量部、反応温度が２３０℃であること以外は前記の実施例６と同 様に実施して重合体を製造し、これらの物性を次の表２に示す。Example file 63 parts by weight of ammonium hydrogen carbonate as imidization substance, as imidization reaction accelerator 60 parts by weight of distilled water, 340 parts by weight of tetrahydrofuran and methylalcohol as a solvent. Same as Example 6 except that 146 parts by weight of coal and the reaction temperature were 230°C. Polymers were prepared according to the same procedure, and their physical properties are shown in Table 2 below.
実施例８ イミド化物質として炭酸水素アンモニウム４７重量部、イミド化反応促進剤とし て蒸留水６０重量部、混合溶媒としてテトラヒドロフラン３４０重量部とメチル アルコール１４６重量部、反応温度が２３０℃であること以外は前記の実施例６ と同様に実施して重合体を製造し、これらの物性を次の表２に示す。Example 8 47 parts by weight of ammonium hydrogen carbonate as imidization substance, as imidization reaction accelerator 60 parts by weight of distilled water, 340 parts by weight of tetrahydrofuran and methyl as a mixed solvent. Example 6 above except that the alcohol was 146 parts by weight and the reaction temperature was 230°C. Polymers were produced in the same manner as above, and their physical properties are shown in Table 2 below.
実施例９ イミド化物質として炭酸水素アンモニウム３１重量部、イミド化反応促進剤とし て蒸留水６０重量部、混合溶媒としてテトラヒドロフラン３４０重量部とメチル アルコール１４６重量部、反応温度が２３０℃であること以外は前記の実施例６ と同様にして実施して重合体を製造し、これらの物性を次の表２に示す。Example 9 31 parts by weight of ammonium hydrogen carbonate as imidization substance, as imidization reaction accelerator 60 parts by weight of distilled water, 340 parts by weight of tetrahydrofuran and methyl as a mixed solvent. Example 6 above except that the alcohol was 146 parts by weight and the reaction temperature was 230°C. Polymers were produced in the same manner as above, and their physical properties are shown in Table 2 below.
実施例１０ イミド化物質として炭酸水素アンモニウム１５重量部、イミド化反応促進剤とし て蒸留水６０重量部、混合溶媒としてテトラヒドロフラン３４０重量部とメチル アルコール１４６重量部、反応温度が２３０℃であること以外は前記の実施例６ と同様に実施して重合体を製造し、これらの物性を次の表２に示す。Example 10 15 parts by weight of ammonium hydrogen carbonate as an imidization substance, as an imidization reaction accelerator 60 parts by weight of distilled water, 340 parts by weight of tetrahydrofuran and methyl as a mixed solvent. Example 6 above except that the alcohol was 146 parts by weight and the reaction temperature was 230°C. Polymers were produced in the same manner as above, and their physical properties are shown in Table 2 below.
比較例２ ＰＭＭＡ１００重量部、イミド化物質としてシクロヘキシルアミン５８重量部、 テトラヒドロフラン４５６重量部、メチルアルコール５８重量部を使用したこと 以外は前記の実施例６と同様に実施して重合体を製造し、これらの物性を次の表 ２に示す。Comparative example 2 100 parts by weight of PMMA, 58 parts by weight of cyclohexylamine as an imidization substance, 456 parts by weight of tetrahydrofuran and 58 parts by weight of methyl alcohol were used. Except for this, a polymer was produced in the same manner as in Example 6 above, and its physical properties are shown in the table below. Shown in 2.
比較例３ ＭＭＡ重合体１００重量部、イミド化物質として炭酸水素アンモニウム６３重量 部、テトラヒドロフラン３４０重量部、メチルアルコール１４６重量部を使用し たこと以外は前記の実施例７と同様に実施して重合体を製造し、これらの物性を 次の表２に示す。Comparative example 3 100 parts by weight of MMA polymer, 63 parts by weight of ammonium hydrogen carbonate as an imidization substance parts, 340 parts by weight of tetrahydrofuran, and 146 parts by weight of methyl alcohol. Except for the above, a polymer was produced in the same manner as in Example 7 above, and its physical properties were determined. It is shown in Table 2 below.
比較例４ ＭＭＡ重合体１００重量部、イミド化物質として炭酸水素アンモニウム４７重量 部、テトラヒドロフラン３４０重量部、メチルアルコール１４６重量部を使用し たこと以外は前記の実施例８と同様に実施して重合体を製造し、これらの物性を 次の表２に示す。Comparative example 4 100 parts by weight of MMA polymer, 47 parts by weight of ammonium hydrogen carbonate as an imidization substance parts, 340 parts by weight of tetrahydrofuran, and 146 parts by weight of methyl alcohol. Except for the above, a polymer was produced in the same manner as in Example 8 above, and its physical properties were determined. It is shown in Table 2 below.
比較例５ ＭＭＡ重合体１００重量部、イミド化物質として炭酸水素アンモニウム３１重量 部、テトラヒドロフラン３４０重量部、メチルアルコール１４６重量部を使用し たこと以外は前記の実施例９と同様に実施して重合体を製造し、これらの物性を 次の表２に示す。Comparative example 5 100 parts by weight of MMA polymer, 31 parts by weight of ammonium hydrogen carbonate as an imidization substance parts, 340 parts by weight of tetrahydrofuran, and 146 parts by weight of methyl alcohol. Except for the above, a polymer was produced in the same manner as in Example 9 above, and its physical properties were determined. It is shown in Table 2 below.
比較例６ ＭＭＡ重合体１００重量部、イミド化物質として炭酸水素アンモニウム１５重量 部、テトラヒドロフラン３４０重量部、メチルアルコール１４６重量部を使用し たこと以外は前記の実施例１０と同様に実施して重合体を製造したし、これらの 物性を次の表２に示す。Comparative example 6 100 parts by weight of MMA polymer, 15 parts by weight of ammonium hydrogen carbonate as an imidization substance parts, 340 parts by weight of tetrahydrofuran, and 146 parts by weight of methyl alcohol. Except for the above, a polymer was produced in the same manner as in Example 10 above, and these The physical properties are shown in Table 2 below.
比較例７ ＭＭＡ重合体１００重量部、イミド化物質として炭酸水素アンモニウム６３重量 部、蒸留水２５重量部、テトラヒドロフラン３４０重量部、メチルアルコール１ ４６重量部を使用したこと以外は前記の実施例７と同様に実施して重合体を製造 し、これらの物性を次の表２に示す。Comparative example 7 100 parts by weight of MMA polymer, 63 parts by weight of ammonium hydrogen carbonate as an imidization substance parts, 25 parts by weight of distilled water, 340 parts by weight of tetrahydrofuran, 1 part by weight of methyl alcohol A polymer was produced in the same manner as in Example 7 above, except that 46 parts by weight was used. Their physical properties are shown in Table 2 below.
比較例８ ＭＭＡ重合体１００重量部、イミド化物質として炭酸水素アンモニウム６３重量 部、蒸留水２５０重量部、テトラヒドロフラン３４０重量部、メチルアルコール １４６重量部を使用したこと以外は前記の実施例７と同様に実施して重合体を製 造し、これらの物性を次の表２に示す。Comparative example 8 100 parts by weight of MMA polymer, 63 parts by weight of ammonium hydrogen carbonate as an imidization substance parts, 250 parts by weight of distilled water, 340 parts by weight of tetrahydrofuran, methyl alcohol A polymer was produced in the same manner as in Example 7 above, except that 146 parts by weight was used. The physical properties are shown in Table 2 below.
比較例９ ＭＭＡ重合体１００重量部、イミド化物質として炭酸水素アンモニウム６３重量 部、蒸留水３８０重量部を使用したこと以外は前記の実施例７と同様に実施して 重合体を製造し、これらの物性を次の表２に示す。Comparative example 9 100 parts by weight of MMA polymer, 63 parts by weight of ammonium hydrogen carbonate as an imidization substance The procedure was carried out in the same manner as in Example 7 above, except that 380 parts by weight of distilled water were used. Polymers were prepared and their physical properties are shown in Table 2 below.
ｆｉ−≦１ １１１重合体が攪拌軸に凝り固まって塊を形成してガラス転移温度の測定不可。fi-≦1 The 111 polymer solidified on the stirring shaft and formed a lump, making it impossible to measure the glass transition temperature.
実施例１１ メチルメタクリレート重合体［（株）ラッキー、ＩＨ−８３０］１００重量部、 イミド化物質として炭酸水素アンモニウム３９重量部、触媒としてテトラメチル アンモニウムヒドロキシドペンタヒトレート９重量部、混合溶媒としてテトラヒ ドロフラン（ＴＨＦ）４５５重量部とメチルアルコール５５重量部を１．８１容 量の高温、高圧用オートクレーブ反応器に投入させた後、反応混合物を２５０ ｒｐＩＤで撹拌してから溶解させて２１０℃で３時間（内圧５５０ｐｓｉ）反応 させた。次いで、反応が完結された後、メチルメタクリルイミド基含有重合体が 含まれた溶液をｎ−ヘキサンに沈澱させた後、濾過して真空状態及び１００℃の 温度で十分に乾燥した結果、白い粉末状態の重合体を得た。この時、得られた重 合体を赤外線スペクトルで測定した結果、１６８０ｃｍ−Ｉ、１７００ｃｍ−’ 及び１７２０ｃｍ−’でメチルメタクリルイミド構造の特性帯が現れてメチルメ タクリルイミド重合体を確認した。この重合体の物性測定の結果は次の表３に示 す。Example 11 Methyl methacrylate polymer [Lucky Co., Ltd., IH-830] 100 parts by weight, 39 parts by weight of ammonium hydrogen carbonate as imidization substance, tetramethyl as catalyst 9 parts by weight of ammonium hydroxide pentahydrate, tetrahydrogen as a mixed solvent 1.81 volume of 455 parts by weight of Dorofuran (THF) and 55 parts by weight of methyl alcohol After charging the reaction mixture into a high-temperature, high-pressure autoclave reactor of 250 Stir with rpID, dissolve and react at 210°C for 3 hours (internal pressure 550psi) I let it happen. Then, after the reaction is completed, the methylmethacrylimide group-containing polymer is The contained solution was precipitated in n-hexane, filtered, and incubated in vacuum and at 100°C. As a result of sufficient drying at high temperature, a white powdery polymer was obtained. At this time, the obtained weight As a result of measuring the coalescence in the infrared spectrum, 1680 cm-I, 1700 cm-' At 1720 cm-', a characteristic band of methyl methacrylimide structure appears and the methyl methacrylimide structure appears. A tacrylimide polymer was confirmed. The results of measuring the physical properties of this polymer are shown in Table 3 below. vinegar.
実施例１２ イミド化物質として炭酸水素アンモニウム３９重量部、イミド化反応触媒として テトラエチルアンモニウムヒドロキシド（４０％水溶液）１８−３重量部、混合 溶媒としてテトラヒドロフラン４５５重量部とメチルアルコール５５重量部、反 応温度が２１０℃であること以外は前記の実施例１１と同様に実施して重合体を 製造したし、これらの物性を次の表３に示す。Example 12 39 parts by weight of ammonium hydrogen carbonate as an imidization substance, as an imidization reaction catalyst Tetraethylammonium hydroxide (40% aqueous solution) 18-3 parts by weight, mixed As solvents, 455 parts by weight of tetrahydrofuran and 55 parts by weight of methyl alcohol were used. The polymer was prepared in the same manner as in Example 11 above, except that the reaction temperature was 210°C. The physical properties are shown in Table 3 below.
実施例１３ メチルメタクリレート（ＭＭＡ）５７重量％、無水マレイン酸（ＭＡＨ）２７重 量％、スチレン（ＳＴ）１６重量％及び連鎖移動剤としてｔ−ドデシルメルカプ タンオル０．２重量％を添加して１４５℃で２時間溶液重合（溶媒としてはエチ ルベンゼン）させて共重合体を得た。Example 13 Methyl methacrylate (MMA) 57% by weight, maleic anhydride (MAH) 27% % by weight, 16% by weight of styrene (ST) and t-dodecyl mercap as chain transfer agent. Solution polymerization was carried out at 145°C for 2 hours with the addition of 0.2% by weight of ethanol (ethyl alcohol was used as the solvent). Rubenzene) to obtain a copolymer.
この時、得られたＭＭＡ−ＭＡＨ−５Ｔ共重合体１００重量部にイミド化物質と して炭酸水素アンモニウム４４重量部、イミド化反応触媒としてテトラメチルア ンモニウムヒドロキシドペンタヒドレ−ト１０重量部、混合溶媒としてテトラヒ ドロフラン３８８重量部とメチルアルコール４６重量部を使用し、内圧が５４０ ｐｓｉであること以外は前記の実施例１１と同様に実施して重合体を製造し、こ れらの物性の次の表３に示す。At this time, an imidized substance was added to 100 parts by weight of the obtained MMA-MAH-5T copolymer. and 44 parts by weight of ammonium hydrogen carbonate, and tetramethyl acetate as an imidization reaction catalyst. 10 parts by weight of ammonium hydroxide pentahydrate, tetrahydrogen as a mixed solvent Using 388 parts by weight of Dorofuran and 46 parts by weight of methyl alcohol, the internal pressure was 540. A polymer was produced in the same manner as in Example 11 above, except that the psi was Their physical properties are shown in Table 3 below.
実施例１４ 実施例１３から製造させたＭＭＡ−ＭＡＲ−ＳＴ共重合体１００重量部、イミド 化物質として炭酸水素アンモニウム４４重量部、イミド化反応触媒としてテトラ エチルアンモニウムヒドロキシド（４０％水溶液）１９重量部、混合溶媒として テトラヒドロフラン３８８重量部とメチルアルコール４６重量部を使用し、内圧 が５６０ｐｓｉであること以外は前記の実施例１１と同様にして重合体を製造し 、これらの物性を次の表３に示す。Example 14 100 parts by weight of MMA-MAR-ST copolymer prepared from Example 13, imide 44 parts by weight of ammonium hydrogen carbonate as a reaction substance, and tetra as an imidization reaction catalyst. 19 parts by weight of ethyl ammonium hydroxide (40% aqueous solution) as a mixed solvent Using 388 parts by weight of tetrahydrofuran and 46 parts by weight of methyl alcohol, the internal pressure was The polymer was prepared in the same manner as in Example 11 above, except that the pressure was 560 psi. , these physical properties are shown in Table 3 below.
比較例１０ メチルメタクリレート重合体１００重量部、イミド化物質として炭酸水素アンモ ニウム３９重量部、混合溶媒としてテトラヒドロフラン４５５重量部とメチルア ルコール５５重量部、反応温度が２１０℃、内圧が５００ｐｓｉであること以外 は前記の実施例１１と同様に実施して重合体を製造し、これらの物性を次の表３ に示す。Comparative example 10 100 parts by weight of methyl methacrylate polymer, ammonium bicarbonate as imidization substance 39 parts by weight of aluminum, 455 parts by weight of tetrahydrofuran and methyl alcohol as a mixed solvent. Except that the alcohol is 55 parts by weight, the reaction temperature is 210°C, and the internal pressure is 500 psi. A polymer was produced in the same manner as in Example 11 above, and the physical properties are shown in Table 3 below. Shown below.
比較例１１ 実施例１３から製造されたＭＭＡ−ＭＡＲ−ＳＴ共重合体１００重量部、イミド 化物質として炭酸水素アンモニウム４４重量部、混合溶媒としてテトラヒドロフ ラン３８２重量部とメチルアルコール４６重量部を使用し、内圧が５００ ｐｓ ｉであること以外は前記の実施例１１と同様に実施して重合体を製造し、これら の物性を次の表３に示す。Comparative example 11 100 parts by weight of MMA-MAR-ST copolymer prepared from Example 13, imide 44 parts by weight of ammonium hydrogen carbonate as a chemical substance, and tetrahydrofuran as a mixed solvent. Using 382 parts by weight of Run and 46 parts by weight of methyl alcohol, the internal pressure was 500 ps. Polymers were produced in the same manner as in Example 11 above, except that i. The physical properties of are shown in Table 3 below.
Ｕ 実施例１５ メチルメタクリレート重合体［（株）ラッキー、ＩＨ−８３０］１００重量部、 イミド化物質としてメチルアミン１４重量部、触媒としてテトラメチルアンモニ ウムヒドロキシドペンタヒドレート７重量部、蒸留水１９重量部、混合溶媒とし てテトラヒドロフラン４５５重量部とメチルアルコール５５重量部を１．８７！ オ一トクレーブ反応器に投入した後、この反応の混合物を撹拌しながら酸化防止 のために窒素を十分に還流させた。次いで、前記の反応の混合物を２５Ｏｒｐｍ で撹拌してから、溶解させて１７０℃で３時間（内圧２００ｐｓｉ）反応させ、 反応が完結された後、メチルメタクリルイミド基含有重合体が含まれた溶液をｎ −ヘキサンに再沈澱させた後、濾過して真空状態及び１００℃の温度で十分に乾 燥した結果、白い粉末状態の重合体を得た。この時、得られた重合体を赤外線ス ペクトルで測定した結果、１６８０ｃｍ−１，１７２０ｃｍ−’でメタクリルイ ミド構造の特性帯が現れてメチルメタクリルイミド重合体を確認した。この重合 体の物性測定の結果は次の表４に示す。U Example 15 Methyl methacrylate polymer [Lucky Co., Ltd., IH-830] 100 parts by weight, 14 parts by weight of methylamine as imidization substance, tetramethylammonium as catalyst 7 parts by weight of hydroxide pentahydrate, 19 parts by weight of distilled water, as a mixed solvent Add 455 parts by weight of tetrahydrofuran and 55 parts by weight of methyl alcohol to 1.87 parts by weight! After being added to the autoclave reactor, the reaction mixture is stirred to prevent oxidation. Nitrogen was thoroughly refluxed for this purpose. The mixture of the above reaction was then heated to 25 Orpm. After stirring, dissolve and react at 170°C for 3 hours (internal pressure 200psi). After the reaction is completed, the solution containing the methylmethacrylimide group-containing polymer is - After reprecipitation in hexane, filter and thoroughly dry in vacuum and at a temperature of 100°C. As a result of drying, a white powdery polymer was obtained. At this time, the obtained polymer was As a result of spectral measurement, methacrylic A characteristic band of mido structure appeared, confirming methylmethacrylimide polymer. This polymerization The results of measuring the physical properties of the body are shown in Table 4 below.
実施例１６ 反応温度が１９０℃であること以外は前記の実施例ｆ１５と同様１二実施して重 合体を製造し、これらの物性を次の表４に示す。Example 16 The same procedure as in Example f15 was repeated except that the reaction temperature was 190°C. Coalesces were prepared and their physical properties are shown in Table 4 below.
実施例１７ 反応温度が２１０℃であること以外は前記の実施例１５と同様に実施して重合体 を製造し、これらの物性を次の表４に示す。Example 17 The polymer was prepared in the same manner as in Example 15 above except that the reaction temperature was 210°C. were produced, and their physical properties are shown in Table 4 below.
比較例１２ 触媒を使用せず、反応温度が１７０°Ｃであること以外は前記の実施例１５と同 様に実施して重合体を製造し、これらの物性を次の表反応温度が１９０℃である こと以外は前記の実施例１５と同様（こ実施して重合体を製造し、これらの物性 を次の表４１こ示す。Comparative example 12 Same as Example 15 above except that no catalyst was used and the reaction temperature was 170°C. Polymers were prepared using the same method, and their physical properties were shown in the following table, when the reaction temperature was 190°C. Other than that, the same as in Example 15 above (this was carried out to produce a polymer, and its physical properties were is shown in Table 41 below.
比較例１４ 触媒を使用せず、反応温度が２１０℃であること以外は前記の実施例１５と同様 に実施して重合体を製造し、これらの物性を次の表４に示す。Comparative example 14 Same as Example 15 above except that no catalyst was used and the reaction temperature was 210°C. Polymers were produced using the following method, and their physical properties are shown in Table 4 below.
ｆ−−２に 実施例１８ 十分に乾燥させたメチルメタクリレート重合体口（株）ラッキー、ＩＨ−８３０ ］１００重量部、イミド化物質として無水シクロヘキシルアミン５７重量部、触 媒としてテトラメチルアンモニウムヒドロキシド（メチルアルコール中２５％） ８．２重量部、混合溶媒として無水条件のテトラヒドロフラン４５５重量部と無 水条件のメチルアルコール５５重量部を１．８１オ一トクレーブ反応器に投入し た後、この反応の混合物を撹拌しながら酸化防止のために窒素を十分に還流させ た。次いで、前記の反応の混合物を２５０ ｒｐｎ＋で撹拌してから溶解させて １９０℃で３時間（内圧２５０ｐｓｉ）反応させ、反応が完結した後、メチルメ タクリルイミド基含有重合体が含まれた溶液をｎ−ヘキサンに再沈澱させた後、 濾過して真空状態及び１００℃の温度で十分に乾燥した結果、白い粉末状態の重 合体を得た。f--2 Example 18 Sufficiently dried methyl methacrylate polymer, manufactured by Lucky Co., Ltd., IH-830 ] 100 parts by weight, 57 parts by weight of anhydrous cyclohexylamine as an imidization substance, Tetramethylammonium hydroxide (25% in methyl alcohol) as vehicle 8.2 parts by weight, 455 parts by weight of anhydrous tetrahydrofuran as a mixed solvent and 55 parts by weight of methyl alcohol in water condition was put into a 1.81 otoclave reactor. After stirring, the reaction mixture was thoroughly refluxed with nitrogen to prevent oxidation. Ta. The mixture of the above reaction was then stirred at 250 rpm+ before dissolving. The reaction was carried out at 190°C for 3 hours (internal pressure 250psi), and after the reaction was completed, the methylmethane After reprecipitating the solution containing the tacrylimide group-containing polymer in n-hexane, As a result of filtration and thorough drying in a vacuum state at a temperature of 100°C, a heavy white powder was obtained. Obtained union.
この時、得られた重合体を赤外線スペクトルで測定した結果、１６８０ｃｍ−１ ，１７０Ｑｃｍ−’及び１７２０ｃｍ−’でメチルメタクリルイミド構造の特性 帯が現れてメチルメタクリルイミド重合体を確認した。この重合体の物性測定の 結果は次の表５に示す。At this time, the obtained polymer was measured by infrared spectrum, and the result was 1680 cm-1 , 170Qcm-' and 1720cm-' A band appeared, confirming the methylmethacrylimide polymer. Measurement of physical properties of this polymer The results are shown in Table 5 below.
実施例１９ 十分に乾燥させたメチルメタクリレート重合体［（株）ラッキー、ＩＨ−８３０ ］１００重量部、イミド化物質として無水プロピルアミン３フ重責部、反応触媒 とてテトラメチルアンモニウムヒドロキシド（メチルアルコール中２５％）、混 合溶媒として無水テトラヒドロフラン４５５重量部とメチルアルコール５５重量 部、反応温度が１９０℃（内圧：３００ｐｓｉ）であること以外は前記の実施例 １８と同様に実施して重合体を製造し、これらの物性を次の表５に示す。Example 19 Thoroughly dried methyl methacrylate polymer [Lucky Co., Ltd., IH-830] ] 100 parts by weight, 3 parts of anhydrous propylamine as imidization substance, reaction catalyst Tetramethylammonium hydroxide (25% in methyl alcohol), mixed 455 parts by weight of anhydrous tetrahydrofuran and 55 parts by weight of methyl alcohol as a combined solvent Example 1, except that the reaction temperature was 190° C. (internal pressure: 300 psi). Polymers were prepared in the same manner as in Example 18, and their physical properties are shown in Table 5 below.
実施例２０ メチルメタクリレート（ＭＭＡ）５７重量％、無水マレイン酸（ＭＡＲ）２７重 量％、スチレン（ＳＴ）１６重量％及びｔ−ドデシルメルカプタン０．２重量％ を添加して１４５℃で２時間溶液中で（溶媒としてはエチルベンゼン）重合させ て共重合体を得た。Example 20 Methyl methacrylate (MMA) 57% by weight, maleic anhydride (MAR) 27% by weight % by weight, 16% by weight of styrene (ST) and 0.2% by weight of t-dodecylmercaptan. was added and polymerized in solution at 145°C for 2 hours (ethylbenzene as solvent). A copolymer was obtained.
この時、得られた完全に乾燥されたＭＭＡ−ＭＡＲ−３Ｔ共重合体１００重量部 、イミド化物質として無水シクロヘキシルアミン６８重量部、触媒としてテトラ メチルアンモニウムヒドロキシドロ。At this time, 100 parts by weight of the completely dried MMA-MAR-3T copolymer obtained , 68 parts by weight of anhydrous cyclohexylamine as an imidized substance, and tetra as a catalyst. Methylammonium Hydroxydro.
９重量部、反応温度が１９０℃（内圧２６０ｐｓｉ）、無水メチルアルコール４ ６重量部であること以外は前記の実施例１８と同様に実施して重合体を製造し、 これらの物性を次の表５に示す。9 parts by weight, reaction temperature 190°C (internal pressure 260 psi), anhydrous methyl alcohol 4 A polymer was produced in the same manner as in Example 18 above, except that the amount was 6 parts by weight, These physical properties are shown in Table 5 below.
実施例２１ 前記の実施例２０から製造された完全に乾燥されたＭＭＡ−ＭＡＲ−３Ｔ共重合 体１００重量部、イミド化物質として無水プロピルアミン４１重量部、触媒とし てテトラメチルアンモニウムヒドロキシドロ、９重量部、溶媒として無水テトラ ヒドロフラン３８２重量部、無水メチルアルコール４６重量部、反応温度が１９ ０℃（内圧３００ｐｓｉ）であること以外は前記の実施例１８と同様に実施して 重合体を製造し、これらの物性を次の表５に示す。Example 21 Fully dried MMA-MAR-3T copolymer prepared from Example 20 above 100 parts by weight of body, 41 parts by weight of anhydrous propylamine as an imidization substance, and 41 parts by weight of anhydrous propylamine as a catalyst. 9 parts by weight of tetramethylammonium hydroxydro, anhydrous tetra as a solvent. Hydrofuran 382 parts by weight, anhydrous methyl alcohol 46 parts by weight, reaction temperature 19 The procedure was carried out in the same manner as in Example 18 above, except that the temperature was 0 °C (internal pressure 300 psi). Polymers were prepared and their physical properties are shown in Table 5 below.
実施例２２ 反応温度が２１０℃（内圧４００ｐｓｉ）であること以外は前記の実施例１８と 同様に実施して重合体を製造し、これらの物性を次の表５に示す。Example 22 Same as Example 18 above except that the reaction temperature was 210°C (inner pressure 400psi). Polymers were prepared in the same manner, and their physical properties are shown in Table 5 below.
実施例２３ 反応温度が２１０℃（内圧４５ Ｑｐｓｉ）であること以外は前記の実施例１９ と同様に実施して重合体を製造し、これらの物性を次の表反応温度が２１０°Ｃ （内圧４５０ｐｓｉ）であること以外は前記の実施例２０と同様に実施して重合 体を製造し、これらの物性を次の表反応温度が２１０℃（内圧４５０ｐｓｉ）で あること以外は前記の実施例２１と同様に実施して重合体を製造し、これらの物 性を次の表触媒を添加させないこと以外は前記の実施例１８乃至２５と同様に実 施して重合体を製造し、これらの物性を次の表５に示す。Example 23 Example 19 above except that the reaction temperature was 210°C (internal pressure 45 Qpsi) Polymers were produced in the same manner as above, and their physical properties are shown in the table below at a reaction temperature of 210°C. Polymerization was carried out in the same manner as in Example 20 above, except that the internal pressure was 450 psi. The following table shows the physical properties at a reaction temperature of 210°C (internal pressure 450psi). Polymers were produced in the same manner as in Example 21 above, except for the following. The same procedure as in Examples 18 to 25 above was carried out except that no catalyst was added. The physical properties of the polymers are shown in Table 5 below.
Ｕ 歴【−」ＬＡ籠１と 要 約 書 本発明はアクリル樹脂をイミド化物質であるアンモニア、１級アミンまたはアン モニアや１級アミンを発生させるアンモニア化合物と適当の温度及び溶媒中で触 媒存在または非存在下にイミド化反応させてなることを特徴とする耐熱性透明ア クリル系樹脂の製造方法に関するものである。U History [-” LA basket 1 and Summary book The present invention uses acrylic resin as an imidizing substance such as ammonia, primary amine or ammonia. Contact with an ammonia compound that generates monia or primary amines at an appropriate temperature and solvent. A heat-resistant transparent resin produced by an imidization reaction in the presence or absence of a medium. The present invention relates to a method for producing acrylic resin.
前記の反応生成物はイミド化構造単位を１０重量％以上含む次式（１）： ［式中、Ｒ１、Ｒ２及びＲ３は各々水素原子や炭素数１乃至２０の置換されるか 、あるいは非置換されたアルキル、シクロアルキル、アリール、アラルキリル、 またはアルカリールであるコで示される化合物またはそれらの混合物である。The reaction product has the following formula (1) containing 10% by weight or more of imidized structural units: [In the formula, R1, R2 and R3 are each substituted with a hydrogen atom or a carbon number of 1 to 20] , or unsubstituted alkyl, cycloalkyl, aryl, aralkylyl, or alkaryl, or a mixture thereof.
補正書の翻訳文提出書 （特許法第１８４条の７第１項） １、特許出願の表示 ＰＣＴ／ＫＲ９０１０００２３ ２、発明の名称 耐熱性透明アクリル系樹脂の製造方法 ３、特許出願人 名称 ラッキー・リミテッド ４、代理人 住所 〒５４０ 大阪府大阪市中央区域見２丁目１番６１号ツイン２１ＭＩＤタ ワー内 電話（０６）９４９−１２６１（１）補正書の翻訳文 １ 通 請求の範囲 １．（訂正）アクリル樹脂をイミド化物質である１級アミンまたは１級アミンを 発生させるアンモニア化合物及び５乃至２０重量％の水と溶媒中で、１８０乃至 ３５０℃の温度で反応させることを特徴とする耐熱性透明アクリル系樹脂の製造 方法。Submission of translation of written amendment (Article 184-7, Paragraph 1 of the Patent Act) 1. Display of patent application PCT/KR90100023 2. Name of the invention Method for producing heat-resistant transparent acrylic resin 3. Patent applicant Name Lucky Limited 4. Agent Address: 2-1-61 Twin 21MID, Chuo District, Osaka City, Osaka Prefecture 540 Office phone number: (06) 949-1261 (1) Translation of the written amendment: 1 copy The scope of the claims 1. (Correction) Acrylic resin is imidized with primary amine or primary amine. In a solvent containing an ammonia compound to be generated and 5 to 20% by weight of water, Production of heat-resistant transparent acrylic resin characterized by reaction at a temperature of 350°C Method.
２、アクリル樹脂が、メチルメタクリレート重合体またはメチルメタクリレート とエチレン系不飽和単量体との共重合体であることを特徴とする請求項１に記載 の耐熱性透明アクリル系樹脂の製造方法。2. Acrylic resin is methyl methacrylate polymer or methyl methacrylate and an ethylenically unsaturated monomer, according to claim 1. A method for producing heat-resistant transparent acrylic resin.
３、メチルメタクリレートとエチレン系不飽和単量体との共重合体は、メチルメ タクリレート構造単位を５０重量％以上含むものであることを特徴とする請求項 ２記載の耐熱性透明アクリル系樹脂の製造方法。3. The copolymer of methyl methacrylate and ethylenically unsaturated monomer is A claim characterized in that it contains 50% by weight or more of tacrylate structural units. 2. The method for producing a heat-resistant transparent acrylic resin according to 2.
４、（訂正）１級アミンは、次式（■）：ＲＮＨ２（ｍ） ［式中、Ｒは水素原子、または非置換、または置換されたＣ、−Ｃ２゜のアルキ ル、シクロアルキル、アリール、アラルキル、アルカリール、アリルである］で 示される化合物またはそれらの混合物であることを特徴とする請求項１記載の耐 熱性透明アクリル系樹脂の製造方法。4. (Correction) The primary amine has the following formula (■): RNH2 (m) [In the formula, R is a hydrogen atom, or an unsubstituted or substituted C, -C2° alkyl cycloalkyl, aryl, aralkyl, alkaryl, allyl]. The compound according to claim 1, characterized in that it is a compound shown or a mixture thereof. A method for producing thermal transparent acrylic resin.
５、（訂正）１級アミンを発生させる混合物は、尿素、１，３−ジメチル尿素、 １，３−エチル尿素、酢酸アンモニウム、次式（■）：ＲＮＨ３ＨＣＯ３（ｎ） ［式中、Ｒは水素原子、または非置換、または置換されたＣ、−Ｃ。5. (Correction) The mixture that generates the primary amine is urea, 1,3-dimethylurea, 1,3-ethyl urea, ammonium acetate, following formula (■): RNH3HCO3 (n) [In the formula, R is a hydrogen atom, or unsubstituted or substituted C, -C.
。のアルキル、シクロアルキル、アリール、アラルキル、アルカリール、アリル であるコで示される炭酸水素アンモニウムまたはその誘導体、またはそれらの混 合物であることを特徴とする請求項１記載の耐熱性透明アクリル系樹脂の製造方 法。. alkyl, cycloalkyl, aryl, aralkyl, alkaryl, allyl Ammonium bicarbonate or its derivatives, or mixtures thereof, represented by The method for producing a heat-resistant transparent acrylic resin according to claim 1, wherein the resin is a compound. Law.
６、（削除） ７、（削除） ８、（訂正）反応生成物が、イミド化構造単位を１０重量％以上含む次式（１） ： ［式中、Ｒは水素原子、または非置換、または置換されたＣ＋ Ｃｚｏのアルキ ル、シクロアルキル、アリール、アラルキル、アルカリール、アリルであるコで 示される化合物またはそれらの混合物であることを特徴とする請求項１記載の耐 熱性透明アクリル系樹脂の製造方法。6. (Delete) 7. (Delete) 8. (Correction) The reaction product contains 10% by weight or more of imidized structural units according to the following formula (1) : [Wherein, R is a hydrogen atom, or an unsubstituted or substituted C+Czo alkyl cycloalkyl, aryl, aralkyl, alkaryl, allyl. The compound according to claim 1, characterized in that it is a compound shown or a mixture thereof. A method for producing thermal transparent acrylic resin.
９、（削除） １０、（削除） １１、（訂正）溶媒が、沸点が５０℃乃至１６０°Ｃであるベンゼン、トルエン 、キシレン、メチルエチルケトン、エチレングリコールジメチルエーテル、ダイ グライム、ダイオキサン、テトラヒドロフラン、ジメチルホルムアミド、ジメチ ルスルホキシド、ジメチルアセトアミド、メチルアルコール、エチルアルコール 、イソプロピルアルコール及びブチルアルコール中から選ばれた１種または２種 以上の混合物であることを特徴とする請求項１記載の耐熱性透明アクリル系樹脂 の製造方法。9. (Delete) 10, (Delete) 11. (Correction) The solvent is benzene or toluene with a boiling point of 50°C to 160°C. , xylene, methyl ethyl ketone, ethylene glycol dimethyl ether, die Grime, dioxane, tetrahydrofuran, dimethylformamide, dimethylene Rusulfoxide, dimethylacetamide, methyl alcohol, ethyl alcohol , one or two selected from isopropyl alcohol and butyl alcohol The heat-resistant transparent acrylic resin according to claim 1, which is a mixture of the above. manufacturing method.
１２、（削除） １３、（削除） １４、（削除） １５、（削除） １６、（削除） １７、（削除） １８、（削除） １９、（削除） ２０、（削除） ２１、（新設）アクリル樹脂をイミド化物質である１級アミンまたは、１級アミ ンを発生させるアンモニア化合物、水１乃至２０重量％及び次式（■）。12, (Delete) 13. (Delete) 14, (Delete) 15, (Delete) 16, (Delete) 17, (Delete) 18, (Delete) 19, (deleted) 20, (deleted) 21. (Newly established) Acrylic resin is imidized with primary amine or primary amine. an ammonia compound that generates ions, 1 to 20% by weight of water, and the following formula (■).
Ｒ，ＮＯＨ（ＩＶ） ［式中、Ｒは水素原子、または非置換、または置換されたＣＩ Ｃ２０のアルキ ル、シクロアルキル、アリール、アラルキル、アルカリール、アリルである］で 示される化合物またはそれらの混合物０゜０１乃至１５重量％と溶媒中で、１０ ０℃乃至３５０°Ｃの温度で反応させることを特徴とする、耐熱性透明アクリル 系樹脂の製造方法。R,NOH(IV) [Wherein, R is a hydrogen atom, or an unsubstituted or substituted CI C20 alkyl cycloalkyl, aryl, aralkyl, alkaryl, allyl]. 10% of the indicated compound or mixture thereof in a solvent with 0.01 to 15% by weight. Heat-resistant transparent acrylic characterized by reacting at temperatures of 0°C to 350°C Method for producing resin.
２２、（新設）アクリル樹脂が、メチルメタクリレート重合体またはメチルメタ クリレートとエチレン系不飽和単量体との共重合体であることを特徴とする請求 項２１記載の耐熱性透明アクリル系樹脂の製造方法。22. (New) Acrylic resin is methyl methacrylate polymer or methyl methacrylate polymer A claim characterized in that it is a copolymer of acrylate and an ethylenically unsaturated monomer. Item 22. The method for producing a heat-resistant transparent acrylic resin.
２３、（新設）メチルメタクリレートとエチレン系不飽和単量体との共重合体が 、メチルメタクリレート単位構造を５０重量％以上含むものであることを特徴と する請求項２２記載の耐熱性透明アクリル系樹脂の製造方法。23. (Newly established) Copolymer of methyl methacrylate and ethylenically unsaturated monomer , containing 50% by weight or more of a methyl methacrylate unit structure. The method for producing a heat-resistant transparent acrylic resin according to claim 22.
２４、（新設）１級アミンが、次式（■）：ＲＮＨ２（ＩＩ［） ［式中、Ｒは水素原子、または非置換、または置換されたＣ、−Ｃ。24, (newly established) primary amine has the following formula (■): RNH2(II[) [In the formula, R is a hydrogen atom, or unsubstituted or substituted C, -C.
。のアルキル、シクロアルキル、アリール、アラルキル、アルカリール、アリル である］で示される化合物またはそれらの混合物であることを特徴とする請求項 ２１記載の耐熱性透明アクリル系樹脂の製造方法。. alkyl, cycloalkyl, aryl, aralkyl, alkaryl, allyl A claim characterized in that it is a compound represented by or a mixture thereof 22. The method for producing a heat-resistant transparent acrylic resin according to 21.
２５、（新設）１級アミンを発生させる化合物が、尿素、１，３−ジメチル尿素 、１．３−エチル尿素、酢酸アンモニウム、次式（ｎ）ＲＮ Ｈｓ ＨＣＯｓ （ＩＦ ） ［式中、Ｒは水素原子、または非置換、または置換されたＣ、−Ｃ２０のアルキ ル、シクロアルキル、アリール、アラルキル、アルカリール、アリルである］で 示される炭酸水素アンモニウムおよびその誘導体またはそれらの混合物であるこ とを特徴とする請求項２１記載の耐熱性透明アクリル系樹脂の製造方法。25. (Newly established) Compounds that generate primary amines include urea and 1,3-dimethylurea. , 1.3-ethyl urea, ammonium acetate, following formula (n) RN Hs HCOs (IF) [Wherein, R is a hydrogen atom, or an unsubstituted or substituted C, -C20 alkyl] cycloalkyl, aryl, aralkyl, alkaryl, allyl]. ammonium bicarbonate and its derivatives or mixtures thereof. The method for producing a heat-resistant transparent acrylic resin according to claim 21.
２６、（新設）溶媒が、沸点が５０℃乃至１６０℃であるベンゼン、トルエン、 キシレン、メチルエチルケトン、エチレングリコールジメチルエーテル、ダイグ ライム、ダイオキサン、テトラヒドロフラン、ジメチルホルムアミド、ジメチル スルホキシド、ジメチルアセトアミド、メチルアルコール、エチルアルコール、 イソプロピルアルコール及びブチルアルコール中から選ばれた１種または２種以 上の混合物であることを特徴とする請求項２１記載の耐熱性透明アクリル系樹脂 の製造方法。26. (Newly established) The solvent has a boiling point of 50°C to 160°C, benzene, toluene, xylene, methyl ethyl ketone, ethylene glycol dimethyl ether, daig Lime, dioxane, tetrahydrofuran, dimethylformamide, dimethyl Sulfoxide, dimethylacetamide, methyl alcohol, ethyl alcohol, One or more selected from isopropyl alcohol and butyl alcohol 22. The heat-resistant transparent acrylic resin according to claim 21, which is a mixture of the above. manufacturing method.
２７、（新設）反応生成物が、イミド化構造単位を５重量％以上含む次式（■） ： ［式中、Ｒは水素原子、または非置換、または置換されたＣＩ Ｃ２゜のアルキ ル、シクロアルキル、アリール、アラルキル、アルカリール、アリルであるコで 示される化合物またはそれらの混合物であることを特徴とする請求項２１記載の 耐熱性透明アクリル系樹脂の製造方法。27. (New) The following formula (■) in which the reaction product contains 5% by weight or more of imidized structural units : [In the formula, R is a hydrogen atom, or an unsubstituted or substituted alkyl group of CI C2°] cycloalkyl, aryl, aralkyl, alkaryl, allyl. 22. The compound according to claim 21, characterized in that it is a compound shown or a mixture thereof. A method for producing heat-resistant transparent acrylic resin.
２８、（新設）アクリル樹脂をイミド化物質である１級アミンまたは１級アミン を発生させるアンモニア化合物及び次式（■）：Ｒ４ＮＯＨ（ＴＶ） ［式中、Ｒは水素原子、または非置換、または置換されたＣ、−Ｃ２゜のアルキ ル、シクロアルキル、アリール、アラルキル、アルカリール、アリルである〕で 示される化合物またはそれらの混合物である、触媒０．０１乃至１５重量％と溶 媒中で、１００℃乃至３５０℃の温度で反応させることを特徴とする、耐熱性透 明アクリル系樹脂の製造方法。28. (Newly established) Acrylic resin is imidized with primary amine or primary amine Ammonia compound that generates and the following formula (■): R4NOH (TV) [In the formula, R is a hydrogen atom, or an unsubstituted or substituted C, -C2° alkyl cycloalkyl, aryl, aralkyl, alkaryl, allyl]. Dissolved with 0.01 to 15% by weight of the catalyst, which is the compound shown or a mixture thereof. A heat-resistant transparent material that is characterized by being reacted in a medium at a temperature of 100°C to 350°C. A method for producing light acrylic resin.
２９、（新設）アクリル樹脂が、メチルメタクリレート重合体やメチルメタクリ レートとエチレン系不飽和単量体との共重合体であることを特徴とする請求項２ ８記載の耐熱性透明アクリル系樹脂の製造方法。29. (Newly established) Acrylic resin is a methyl methacrylate polymer and methyl methacrylate polymer. Claim 2, characterized in that it is a copolymer of a ester and an ethylenically unsaturated monomer. 8. The method for producing a heat-resistant transparent acrylic resin according to 8.
３０、（新設）メチルメタクリレートとエチレン系不飽和単量体との共重合体が 、メチルメタクリレート単位構造を５０重量％以上含むものであることを特徴と する請求項２９記載の耐熱性透明アクリル系樹脂の製造方法。30. (Newly established) Copolymer of methyl methacrylate and ethylenically unsaturated monomer , containing 50% by weight or more of a methyl methacrylate unit structure. The method for producing a heat-resistant transparent acrylic resin according to claim 29.
３１．（新設）１級アミンが、次式（■）：ＲＮＨ２（ｍ） ［式中、Ｒは水素原子、または非置換または置換されたＣ、−Ｃ２゜のアルキル 、シクロアルキル、アリール、アラルキル、アルカリール、アリルである］で示 される化合物またはそれらの混合物であることを特徴とする請求項２８記載の耐 熱性透明アクリル系樹脂の製造方法。31. (Newly established) The primary amine has the following formula (■): RNH2 (m) [In the formula, R is a hydrogen atom, or an unsubstituted or substituted C, -C2° alkyl , cycloalkyl, aryl, aralkyl, alkaryl, allyl] 29. The compound according to claim 28, which is a compound or a mixture thereof. A method for producing thermal transparent acrylic resin.
３２、（新設）１級アミンを発生させる化合物が、尿素、１，３−ジメチル尿素 、１．３−エチル尿素、酢酸アンモニウム、次式（ｎ）ＲＮＨ３ＨＣＯ３（ＩＩ ） ［式中、Ｒは水素原子、または非置換または置換されたＣＩ Ｃ２０のアルキル 、シクロアルキル、アリール、アラルキル、アルカリール、アリルである］で示 される炭酸水素アンモニウムおよびその誘導体、またはそれらの混合物であるこ とを特徴とする請求項２８記載の耐熱性透明アクリル系樹脂の製造方法。32. (Newly established) Compounds that generate primary amines include urea and 1,3-dimethylurea. , 1,3-ethyl urea, ammonium acetate, the following formula (n) RNH3HCO3 (II ) [Wherein, R is a hydrogen atom, or an unsubstituted or substituted CI C20 alkyl , cycloalkyl, aryl, aralkyl, alkaryl, allyl] ammonium bicarbonate and its derivatives, or mixtures thereof. The method for producing a heat-resistant transparent acrylic resin according to claim 28.
３３、（新設）溶媒が、沸点が５０℃乃至１６０℃であるベンゼン、トルエン、 キシレン、メチルエチルケトン、エチレングリコールジメチルエーテル、ダイグ ライム、ダイオキサン、テトラヒドロフラン、ジメチルホルムアミド、ジメチル スルホキシド、ジメチルアセトアミド、メチルアルコール、エチルアルコール、 イソプロピルアルコール及びブチルアルコール中から選ばれた１種または２種以 上の混合物であることを特徴とする請求項２８記載の耐熱性透明アクリル系樹脂 の製造方法。33. (Newly established) The solvent is benzene, toluene, with a boiling point of 50°C to 160°C, xylene, methyl ethyl ketone, ethylene glycol dimethyl ether, daig Lime, dioxane, tetrahydrofuran, dimethylformamide, dimethyl Sulfoxide, dimethylacetamide, methyl alcohol, ethyl alcohol, One or more selected from isopropyl alcohol and butyl alcohol The heat-resistant transparent acrylic resin according to claim 28, which is a mixture of the above. manufacturing method.
３４、（新設）反応生成物が、イミド化構造単位を５重量％以上含む次式（１） ； 〔式中、Ｒは水素原子、または非置換または置換されたＣＩ Ｃ２Ｇのアルキル 、シクロアルキル、アリール、アラルキル、アルカリール、アリルである］で示 される化合物、またはそれらの混合物であることを特徴とする請求項２８記載の 耐熱性透明アクリル系樹脂の製造方法。34. (Newly established) The reaction product contains 5% by weight or more of imidized structural units according to the following formula (1) ; [Wherein, R is a hydrogen atom, or an unsubstituted or substituted CI C2G alkyl , cycloalkyl, aryl, aralkyl, alkaryl, allyl] or a mixture thereof. A method for producing heat-resistant transparent acrylic resin.
３５ （新設）メタクリル樹脂を次式（■）：ＲＮＨ３ＨＣＯ３（ｎ） ［式中、Ｒは水素原子、または非置換または置換されたＣｌＣ２゜のアルキル、 ンクロアルキル、アリー／Ｌ−，アラルキル、アルカリール、アリルである］で 示される炭酸水素アンモニウムまたは１級アミンを発生させるその誘導体または それらの混合物と溶媒中で、１００℃乃至３５０℃の温度で、反応させることを 特徴とする、耐熱性透明アクリル系樹脂の製造方法。35 (Newly established) Methacrylic resin with the following formula (■): RNH3HCO3 (n) [wherein R is a hydrogen atom, or unsubstituted or substituted ClC2° alkyl, cycloalkyl, ary/L-, aralkyl, alkaryl, allyl] ammonium bicarbonate or its derivatives generating primary amines as shown; or React with the mixture in a solvent at a temperature of 100°C to 350°C. A method for producing heat-resistant transparent acrylic resin.
３６ （新設）アクリル樹脂は、メチルメタクリレート重合体やメチルメタクリ レートとエチレン系不飽和単量体との共重合体であることを特徴とする請求項３ ５記載の耐熱性透明アクリル系樹脂の製造方法。36 (Newly established) Acrylic resin is a methyl methacrylate polymer or methyl methacrylate polymer. Claim 3, characterized in that it is a copolymer of a ester and an ethylenically unsaturated monomer. 5. The method for producing a heat-resistant transparent acrylic resin according to 5.
３７ （新設）メチルメタクリレートとエチレン系不飽和単量体との共重合体が 、メチルメタクリレート単位構造を５０重量％以上含むものであることを特徴と する請求項３６記載の耐熱性透明アクリル系樹脂の製造方法。37 (Newly established) Copolymer of methyl methacrylate and ethylenically unsaturated monomer , containing 50% by weight or more of a methyl methacrylate unit structure. The method for producing a heat-resistant transparent acrylic resin according to claim 36.
３８、（新設）溶媒が、沸点が５０℃乃至１６０℃であるベンゼン、トルエン、 キシレン、メチルエチルケトン、エチレングリコールジメチルエーテル、ダイグ ライム、グイオキサン、テトラヒドロフラン、ジメチルホルムアミド、ジメチル スルホキシド、ジメチルアセトアミド、メチルアルコール、エチルアルコール、 イソプロピルアルコール及びブチルアルコール中から選ばれた１種または２種以 上の混合物であることを特徴とする請求項３５記載の耐熱性透明アクリル系樹脂 の製造方法。38. (Newly established) The solvent has a boiling point of 50°C to 160°C, benzene, toluene, xylene, methyl ethyl ketone, ethylene glycol dimethyl ether, daig Lime, guioxane, tetrahydrofuran, dimethylformamide, dimethyl Sulfoxide, dimethylacetamide, methyl alcohol, ethyl alcohol, One or more selected from isopropyl alcohol and butyl alcohol 36. The heat-resistant transparent acrylic resin according to claim 35, which is a mixture of the above. manufacturing method.
３９、（新設）反応生成物が、イミド化構造単位を５重量％以上含む次式（１） ： ［式中、Ｒは水素原子、または非置換または置換されたｃ、Ｃ２０のアルキル、 シクロアルキル、アリール、アラルキル、アルカリール、アリルである］で示さ れる化合物またはそれらの混合物であることを特徴とする請求項３５に記載の耐 熱性透明アクリル系樹脂の製造方法。39, (Newly established) The reaction product contains 5% by weight or more of imidized structural units according to the following formula (1) : [wherein R is a hydrogen atom, or unsubstituted or substituted c, C20 alkyl, cycloalkyl, aryl, aralkyl, alkaryl, allyl] 36. The resistant compound according to claim 35, characterized in that it is a compound or a mixture thereof. A method for producing thermal transparent acrylic resin.
４０、（新設）アクリル樹脂を式（ｎ）で示される炭酸水素アンモニウムまたは １級アミンを発生させるその誘導体及び次式：％式％（） ［式中、Ｒは水素原子、または非置換または置換されたｃ、Ｃ２０のアルキル、 シクロアルキル、アリール、アラルキル、アルカリール、アリルである］で示さ れる化合物またはそれらの混合物である、触媒０．０１乃至１５重量％と溶媒中 で、１００’Ｃ乃至３５０’Ｃの温度で反応させることを特徴とする、耐熱性透 明アクリル系樹脂の製造方法。40, (Newly established) Acrylic resin with ammonium hydrogen carbonate or Derivatives thereof that generate primary amines and the following formula: % formula % () [wherein R is a hydrogen atom, or unsubstituted or substituted c, C20 alkyl, cycloalkyl, aryl, aralkyl, alkaryl, allyl] in a solvent with 0.01 to 15% by weight of a catalyst, or a mixture thereof. A heat-resistant transparent material characterized by being reacted at a temperature of 100'C to 350'C. A method for producing light acrylic resin.
４１、（新設）アクリル樹脂が、メチルメタクリレート重合体やメチルメタクリ レートとエチレン系不飽和単量体との共重合体であることを特徴とする請求項４ ０記載の耐熱性透明アクリル系樹脂の製造方法。41. (Newly established) Acrylic resin is a methyl methacrylate polymer and methyl methacrylate polymer. Claim 4, characterized in that it is a copolymer of a ester and an ethylenically unsaturated monomer. A method for producing a heat-resistant transparent acrylic resin according to 0.
４２、（新設）メチルメタクリレートとエチレン系不飽和単量体との共重合体が 、メチルメタクリレート単位構造を５０重量％以上含むものであることを特徴と する請求項４１記載の耐熱性透明アクリル系樹脂の製造方法。42. (Newly established) Copolymer of methyl methacrylate and ethylenically unsaturated monomer , containing 50% by weight or more of a methyl methacrylate unit structure. The method for producing a heat-resistant transparent acrylic resin according to claim 41.
４３、（新設）溶媒が、沸点が５０℃乃至１６０℃であるベンゼン、トルエン、 キシレン、メチルエチルケトン、エチレングリコールジメチルエーテル、グイグ ライム、ダイオキサン、テトラヒドロフラン、ジメチルホルムアミド、ジメチル スルホキシド、ジメチルアセトアミド、メチルアルコール、エチルアルコール、 イソプロピルアルコール及びブチルアルコール中から選ばれた１種または２種以 上の混合物であることを特徴とする請求項４０記載の耐熱性透明アクリル系樹脂 の製造方法。43. (Newly established) The solvent has a boiling point of 50°C to 160°C, benzene, toluene, Xylene, methyl ethyl ketone, ethylene glycol dimethyl ether, Guigu Lime, dioxane, tetrahydrofuran, dimethylformamide, dimethyl Sulfoxide, dimethylacetamide, methyl alcohol, ethyl alcohol, One or more selected from isopropyl alcohol and butyl alcohol 41. The heat-resistant transparent acrylic resin according to claim 40, which is a mixture of the above. manufacturing method.
４４、（新設）反応生成物が、イミド化構造単位を５重量％以上含む次式（１） ： ［式中、Ｒは水素原子、または非置換または置換されたＣ、−Ｃ２゜のアルキル 、シクロアルキル、アリ二ノラアラルキル、アルカリール、アリルである］で示 される化合物またはそれらの混合物であることを特徴とする請求項４０記載の耐 熱性透明アクリル系樹脂の製造方法。44, (Newly established) The reaction product contains 5% by weight or more of imidized structural units according to the following formula (1) : [In the formula, R is a hydrogen atom, or an unsubstituted or substituted C, -C2° alkyl , cycloalkyl, albinolaaralkyl, alkaryl, allyl] or a mixture thereof. A method for producing thermal transparent acrylic resin.
国際調査報告 い１１．＾１１．−灯／にＲ匍ｌω車３international search report 11. ^11. -Light/Ni R ω car 3
Claims (20)
Applications Claiming Priority (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR89/20194 | 1989-12-29 | ||
| KR1019890020194A KR930005998B1 (en) | 1989-12-29 | 1989-12-29 | Process for preparing acrylic group resin having heat resistance and good transparency |
| KR1019890020345A KR930005999B1 (en) | 1989-12-30 | 1989-12-30 | Process for preparing acrylic |
| KR89/20345 | 1989-12-30 | ||
| KR90/12454 | 1990-08-13 | ||
| KR1019900012452A KR930006079B1 (en) | 1990-08-13 | 1990-08-13 | Process for preparing acrylic group resin having good heat resistance and transparency |
| KR1019900012454A KR930006081B1 (en) | 1990-08-13 | 1990-08-13 | Process for preparing acrylic group resin having good heat resistance and transparency |
| KR90/12452 | 1990-08-13 | ||
| KR1019900012453A KR930006080B1 (en) | 1990-08-13 | 1990-08-13 | Process for preparing acrylic group resin having good heat resistance and transparency |
| KR90/12453 | 1990-08-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04504878A true JPH04504878A (en) | 1992-08-27 |
| JP2607789B2 JP2607789B2 (en) | 1997-05-07 |
Family
ID=27532119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3501368A Expired - Fee Related JP2607789B2 (en) | 1989-12-29 | 1990-12-28 | Method for producing heat-resistant transparent acrylic resin |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5369189A (en) |
| EP (1) | EP0461224B1 (en) |
| JP (1) | JP2607789B2 (en) |
| AT (1) | ATE142653T1 (en) |
| DE (1) | DE69028521T2 (en) |
| DK (1) | DK0461224T3 (en) |
| ES (1) | ES2091905T3 (en) |
| GR (1) | GR3021538T3 (en) |
| WO (1) | WO1991009886A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006337491A (en) * | 2005-05-31 | 2006-12-14 | Kaneka Corp | Polarizer protecting film and polarizing plate using same |
| JP2006337492A (en) * | 2005-05-31 | 2006-12-14 | Kaneka Corp | Polarizer protecting film and polarizing plate using same |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5126409A (en) * | 1991-01-08 | 1992-06-30 | Rohm And Haas Company | Polyglutarimides with improved properties |
| DE4142575A1 (en) * | 1991-12-21 | 1993-06-24 | Basf Ag | POLY (METH) ACRYLIMIDE |
| DE4142572A1 (en) * | 1991-12-21 | 1993-06-24 | Basf Ag | N-ARYL SUBSTITUTED POLY (METH) ACRYLIMIDES |
| NL9200305A (en) * | 1992-02-19 | 1993-09-16 | Dsm Nv | METHOD FOR MANUFACTURING A COPOLYMER CONTAINING VINYLAROMATIC UNITS AND MALEIMIDE UNITS |
| FR2694562B1 (en) * | 1992-08-04 | 1994-10-28 | Atochem Elf Sa | New process for the preparation of modified methyl methacrylate (MAM) polymers or copolymers. |
| KR100682237B1 (en) | 2005-02-07 | 2007-02-15 | 주식회사 엘지화학 | Method for preparing imidized copolymer resin |
| US9329486B2 (en) | 2005-10-28 | 2016-05-03 | Dynaloy, Llc | Dynamic multi-purpose composition for the removal of photoresists and method for its use |
| US8263539B2 (en) * | 2005-10-28 | 2012-09-11 | Dynaloy, Llc | Dynamic multi-purpose composition for the removal of photoresists and methods for its use |
| US7632796B2 (en) | 2005-10-28 | 2009-12-15 | Dynaloy, Llc | Dynamic multi-purpose composition for the removal of photoresists and method for its use |
| TWI450052B (en) | 2008-06-24 | 2014-08-21 | Dynaloy Llc | Stripper solutions effective for back-end-of-line operations |
| US8987181B2 (en) | 2011-11-08 | 2015-03-24 | Dynaloy, Llc | Photoresist and post etch residue cleaning solution |
| US9158202B2 (en) | 2012-11-21 | 2015-10-13 | Dynaloy, Llc | Process and composition for removing substances from substrates |
| US9029268B2 (en) | 2012-11-21 | 2015-05-12 | Dynaloy, Llc | Process for etching metals |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2146209A (en) * | 1936-07-31 | 1939-02-07 | Du Pont | Preparation of resinous imides of substituted acrylic acids |
| DE1088231B (en) * | 1958-03-22 | 1960-09-01 | Roehm & Haas Gmbh | Process for the preparation of nitrogen-containing derivatives of polymethacrylic acid |
| CA1106541A (en) * | 1975-11-19 | 1981-08-04 | Richard M. Kopchik | Imidized acrylic polymers |
| US4169924A (en) * | 1977-06-09 | 1979-10-02 | Gaf Corporation | Preparation of linear cyclic polyimides from latices |
| US4246374A (en) * | 1979-04-23 | 1981-01-20 | Rohm And Haas Company | Imidized acrylic polymers |
| FR2508466B1 (en) * | 1981-06-25 | 1986-09-12 | Du Pont | PROCESS FOR THE PREPARATION OF IMIDIZED ACRYLIC POLYMERS |
| CA1277095C (en) * | 1985-05-01 | 1990-11-27 | Hideaki Makino | Process for preparing methacrylimide-containing polymers |
| CA1279747C (en) * | 1986-01-23 | 1991-01-29 | Hisao Anzai | Methacrylate resin composition and process for its preparation |
| IT1223052B (en) * | 1987-11-04 | 1990-09-12 | Vedril Spa | IMMIDIZED ACRYLIC POLYMERS AND PROCEDURE FOR THEIR PREPARATION |
| JPH0264108A (en) * | 1988-08-30 | 1990-03-05 | Mitsubishi Rayon Co Ltd | Production of methacryloylimide group-containing polymer and light transmission fiber containing the polymer obtained by the same production as constituent component |
| JPH02178309A (en) * | 1988-12-29 | 1990-07-11 | Mitsubishi Rayon Co Ltd | Methacrylimide-containing polymer |
| JP3176944B2 (en) * | 1991-03-11 | 2001-06-18 | 三菱レイヨン株式会社 | Methacrylimide group-containing polymer |
-
1990
- 1990-12-28 ES ES91900956T patent/ES2091905T3/en not_active Expired - Lifetime
- 1990-12-28 EP EP91900956A patent/EP0461224B1/en not_active Expired - Lifetime
- 1990-12-28 DE DE69028521T patent/DE69028521T2/en not_active Expired - Fee Related
- 1990-12-28 WO PCT/KR1990/000023 patent/WO1991009886A1/en active IP Right Grant
- 1990-12-28 DK DK91900956.3T patent/DK0461224T3/en active
- 1990-12-28 US US07/773,896 patent/US5369189A/en not_active Expired - Fee Related
- 1990-12-28 AT AT91900956T patent/ATE142653T1/en not_active IP Right Cessation
- 1990-12-28 JP JP3501368A patent/JP2607789B2/en not_active Expired - Fee Related
-
1996
- 1996-11-06 GR GR960402912T patent/GR3021538T3/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006337491A (en) * | 2005-05-31 | 2006-12-14 | Kaneka Corp | Polarizer protecting film and polarizing plate using same |
| JP2006337492A (en) * | 2005-05-31 | 2006-12-14 | Kaneka Corp | Polarizer protecting film and polarizing plate using same |
| JP4695439B2 (en) * | 2005-05-31 | 2011-06-08 | 株式会社カネカ | Polarizer protective film and polarizing plate using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2091905T3 (en) | 1996-11-16 |
| DK0461224T3 (en) | 1996-10-28 |
| EP0461224B1 (en) | 1996-09-11 |
| EP0461224A1 (en) | 1991-12-18 |
| ATE142653T1 (en) | 1996-09-15 |
| DE69028521D1 (en) | 1996-10-17 |
| JP2607789B2 (en) | 1997-05-07 |
| DE69028521T2 (en) | 1997-01-30 |
| US5369189A (en) | 1994-11-29 |
| WO1991009886A1 (en) | 1991-07-11 |
| GR3021538T3 (en) | 1997-02-28 |
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